10 1021@acs Chemrev 5b00373

Review
pubs.acs.org/CR
Surface Organometallic and Coordination Chemistry toward SingleSite Heterogeneous Catalysts: Strategies, Methods, Structures, and
Activities
Christophe Coperet,*, Aleix Comas-Vives, Matthew P. Conley, Deven P. Estes, Alexey Fedorov,
Victor Mougel, Haruki Nagae,, Francisco Nunez-Zarur, and Pavel A. Zhizhko,
Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir Prelog Weg 15, CH-8093 Zurich, Switzerland
Department of Chemistry, Graduate School of Engineering Science, Osaka University, CREST, Toyonaka, Osaka 560-8531, Japan
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov str. 28, 119991 Moscow, Russia
S Supporting Information
*
3.4. Stoichiometric Reactivity and Activation of

Small Molecules on Well-Dened Surface
Sites
3.4.1. Stoichiometric Ligand Exchange via
Protonolysis Reactions with Brnsted
Acids
3.4.2. Reactions with Lewis Bases
3.4.3. Coordination and Activation of N2
3.4.4. Activation of O2 and N2O
3.4.5. Activation of CO2
3.4.6. Stoichiometric Reactions with Ketones
3.4.7. Stoichiometric Reactions with Alkanes
4. Catalytic Activity and Applications
4.1. Hydrogenation of Alkenes, Alkynes, and
Arenes
4.2. Metathesis of Alkenes and Alkynes
4.2.1. Alkene Metathesis Using Group 67
Silica-Supported Catalysts
4.2.2. Alkene Metathesis Using Silica-Supported Ru Alkylidenes
4.2.3. Alkene Metathesis with Re and W on
Alumina-Containing Supports
4.2.4. Alkyne Metathesis
4.3. Oxo/Imido Heterometathesis
4.4. Oligomerization of Alkenes
4.4.1. Ethylene Dimerization and Trimerization
4.5. Direct Conversion of Ethylene to Propylene
4.6. Polymerization Reactions
4.6.1. Single-Site Models of ZieglerNatta
Type Catalysts
4.6.2. Single-Site Models for the Phillips
Catalyst
4.6.3. Supported Late Transition Metal Catalysts for the Polymerization of Ethylene
4.6.5. Polymerization of Other Substrates
4.7. Alkane Homologation Processes and Related Reactions
4.7.1. Alkane Hydrogenolysis
4.7.2. Alkane Metathesis
CONTENTS
1. Introduction
2. Concepts, Denitions, Tools, and Practical Considerations
2.1. Concepts and Denitions
2.2. Toolbox of Characterization Methods
2.3. Practical Aspects
2.3.1. Preparation and Characterization of the
Supports (Calcination, Dehydroxylation,
and Passivation)
2.3.2. Grafting
2.3.3. Storage and Handling
3. Description of the Surface Chemistry on Oxides
3.1. General Concepts, Strategy, and Methods
3.2. Structure of Surface Species Resulting from
Grafting of the Molecular Precursors
3.2.1. Silica-Supported Well-Dened Metal
Sites
3.2.2. Alumina-Supported Metal Complexes
3.2.3. SilicaAlumina Supported Metal Complexes
3.2.4. Other Supports
3.3. Evolution of Well-Dened Surface Sites
upon Post-Treatment and/or Functionalization
3.3.1. Calcination
3.3.2. Thermolysis under Vacuum or Inert Gas
3.3.3. Thermal Treatment under H2
3.3.4. Thermal Treatment under H2S
XXXX American Chemical Society
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Received: June 26, 2015
DOI: 10.1021/acs.chemrev.5b00373
Chem. Rev. XXXX, XXX, XXXXXX
Chemical Reviews
4.7.3. Cross-Metathesis of Methane and Higher Alkanes
4.7.4. Nonoxidative Methane Coupling
4.8. Dehydrogenation of Alkanes
4.9. Epoxidation of Alkenes
4.10. Oxidation and Deperoxidation of Alkanes
4.11. Other Selected Catalytic Transformations
4.11.1. Hydroamination
4.11.2. Hydrosilylation
4.11.3. Other Reactions
5. Emerging Fields
5.1. Well-Dened Catalysts through Grafting on
Advanced Functional Materials
5.2. Molecular Approach Beyond Well-Dened
Heterogeneous Catalysts
6. Conclusions
Associated Content
Supporting Information
Author Information
Corresponding Author
Notes
Biographies
Acknowledgments
Dedication
Abbreviation List
References
Review
dened active sites. One powerful approach, known as surface

organometallic chemistry (SOMC),1023 treats the surface of
the catalyst support as a ligand and aims at controlling its
reactivity toward molecular precursors, such as organometallic
or coordination complexes. The grafted molecular complexes
can be used directly in catalysis or transformed after grafting by
a thermal post-treatment under vacuum, inert or reactive gas, or
modied by a postreaction to incorporate new ancillary ligands.
This approach permits well-dened surface species to be
prepared and fully characterized with techniques complementary to those of solution chemistry. SOMC has been employed
since the 1970s to generate single-site catalysts, supportedmetal nanoparticle catalysts, and even extended structures (e.g.,
WS2) from grafted species.14,2432 The main advantage of
SOMC lies in its ability to generate surface sites with a known
coordination sphere, thus facilitating structureactivity relationship studies and rational design of heterogeneous catalysts.
Research in SOMC has gained momentum in the past 20
years, spurred by the need to improve existing catalysts and the
advances in spectroscopic and computational methods, which
allow very detailed structural characterization, an essential step
toward catalyst development through structureactivity
relationship approach. Several reviews and books on SOMC
have been published in the past 15 years.4,1013,1523,3335
However, many new contributions have been reported in the
past decade, creating a need for a comprehensive review
covering these recent advances.
Herein, we present the details of the development of SOMC.
In particular, we describe the synthesis, characterization, and
catalytic activity of well-dened metal species on the surface of
oxide supports, discussing both strategies and methods. We
concentrate the review on transition metal and lanthanide
species because of their importance in catalytic processes;
focusing mainly on data that appeared after 2000. Some main
group element surface chemistry will be discussed in the
context of support modication because of their use as solid
cocatalyst for transition-metal complexes. Zeolites, which have
dierent reactivity due to their microporosity, and supported
metal clusters were recently reviewed and are not included.19,20,3638
This review is divided into four separate sections, each
discussing a dierent aspect of SOMC. In section 2, we
introduce the concepts and oer important practical guidelines
to chemists who would like to enter the eld. In section 3, we
provide a comprehensive list of molecular precursors used and
the corresponding surface species formed upon their grafting.
Section 3 is divided into subsections, each discussing a
particular support type. Within each subsection in section 3,
we classied molecular precursors based on the nature of the
ligand set and the metal. We end section 3 with a discussion of
the eect of post-treatment on the structure of surface species.
In section 4, we discuss the catalytic properties of the
aforementioned surface species in reactions such as hydrogenation, dehydrogenation, polymerization, metathesis, alkane
conversion, and oxidation. In section 5, we give an outlook for
the eld with the appearance of novel functional materials and
possible applications beyond the current scope of research
activities.
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1. INTRODUCTION
The chemical industry relies on catalytic processes, which
involve mainly heterogeneous catalysts because they oer many
advantages over their homogeneous counterparts such as easier
separation of catalysts from reaction products, their applicability
to continuous ow processes, and their recyclability (often by
simply heating in the presence of air or H2).1,2 However,
homogeneous catalysts display several advantages over
heterogeneous catalysts. For example, homogeneous catalysts
are often active at lower temperatures, have higher selectivities,
and are chemically better dened; all active sites have ideally a
known and uniform structure. In particular, the well-dened
nature of their active sites, or at least of the precatalyst
structures, allows for more rational catalyst development
through structureactivity relationships.
Heterogeneous catalysts are usually prepared via the
dispersion of a metal salt/precursor onto a support. These
materials are typically heated under a gas stream, e.g., air, H2, ...,
giving dispersed metal ions with a variable number of MO
bonds between the support and the metal sites or supported
metal particles. Such catalysts contain a broad distribution of
metal coordination environments, and often only a small
fraction of those are active in catalysis. These properties make
characterization at the molecular level dicult, if not
impossible, thereby preventing rational catalyst development.
Thus, the active sites of many heterogeneous catalysts are
matters of intense debate, e.g., the Phillips ethylene polymerization catalyst, ZieglerNatta olen polymerization catalyst,
Caton propane dehydrogenation catalyst, tungsten oxide and
rhenium oxide olen metathesis catalysts, propylene epoxidation catalyst, and vanadyl catalyst for oxidative propane
dehydrogenation, to name but a few.39
To combine the advantages of both homogeneous and
heterogeneous catalysis, research eorts have been directed
toward the generation of heterogeneous catalysts with wellB
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Scheme 1. Dehydroxylation of a metal oxide surface and grafting LnMXx onto MSOH
Table 1. Methods of Characterization and Chemical Information on Surface Sites

method
N2 adsorption
transmission electron microscopy (TEM)
and EDX
X-ray diraction
elemental analysis (EA)
mass balance analysis (MB)

IR spectroscopy
Raman spectroscopy
UVvis
XPS, Auger spectroscopy
Mossbauer spectroscopy
XANES
EXAFS
EPR
solid-state NMR
homogeneous molecular models

computational chemistry
examples of information provided by each method
refs
surface area, porosity

morphologyaggregation statecomposition and distribution of atoms of the solid matrix
1
1
specic polymorph of the support and level of crystallinity

metal and other elements loadings
average composition of surface complexes
stoichiometry of surface functionalization
establishing the stoichiometry of grafting
monitoring of the consumption of reactant and formation of released product
evidence for the disappearance and/or appearance of surface functionalities,
e.g. consumption of surface OH groups and appearance of specic surface
sites (CH, NH, CC, MH vibrations)
quantication of acidic and basic sites by using basic probe molecules (CO, pyridine, MeCN)
characterization of surface oxo and related species
evaluation of the isolation or agglomeration of surface species
metal oxidation state
oxidation state and local geometry for specic elements such as Sn or Fe
metal oxidation state and geometry of surface complexes
coordination sphere of the metal: number, type and bond distance of atoms (ligands) bound to the
metal sites
characterization and titration of paramagnetic species
detailed molecular-level structure
types of ligands bound to the surface sites (usually via 1H, 13C, 15N, 31P NMR)
reaction intermediates using labeled reactants
measurement of acidity (phosphine oxide and pyridine adsorption) with 15N and 31P NMR
discrimination of surface atoms in oxides (e.g., Al2O3, SiO2, etc. with 27Al and 29Si NMR)
structural information on isoelectronic and structural molecular species (bond distances by X-ray and
spectroscopic signatures)
evaluation of structure stability
prediction of spectroscopic signatures
evaluation of reaction pathways
2. CONCEPTS, DEFINITIONS, TOOLS, AND PRACTICAL

CONSIDERATIONS
39,4352
6,45,47,52,53
5258
1
1
1,59,60
1,59,60
1,58
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7782
8385
analysis, and/or mass spectrometry, to name a few common

techniques. Though these methods obviously cannot apply to
well-dened heterogeneous catalysts, there are several spectroscopic tools that give molecular level information about the
catalytically active site.
2.1. Concepts and Denitions
An important step to synthesize heterogeneous catalysts using a

molecular strategy is the understanding of the reactivity of a
support surface toward reactive inorganic species. Metal oxide
supports are terminated by surface MSOH and MSOMS
groups. The types and densities of these groups can be
modied by thermal treatment under vacuum. For example,
treating silica at 700 C under vacuum (105 mbar) forms
SiO2700 that contains ca. 0.8 SiOH nm2.34,4042 These
surfaces react with inorganic complexes in a more predictable
fashion than fully hydroxylated surfaces, as shown in Scheme 1.
With a suciently reactive X anionic ligand, a generic metal
complex LnMXx reacts with MSOH to form MSOMLnXx1
and HX. MSOMLnXx1 can also interact or react with
adjacent MSOMS or Lewis acid sites. MSOMLnXx1 sites
are often referred to as well-dened or single-sites.
In molecular chemistry extensive characterization is required
in order to establish a structure. This is often achieved by
single-crystal X-ray diraction, solution spectroscopy, elemental
2.2. Toolbox of Characterization Methods
A combination of techniques that describes the support and

also addresses the molecular structure of the surface site is
necessary to give a comprehensive understanding of welldened heterogeneous catalysts (Table 1). Powder X-ray
diraction, microscopy, and gas absorption give information
about the bulk structure, morphology, and surface area of the
support. If grafting occurs on MSOH sites, titration of these
groups, which will be described below, can dene the
theoretical maximum loading/coverage of well-dened sites
onto the support. Elemental analysis (EA) and mass balance
(MB) give the stoichiometry of the reaction shown in Scheme
1.
Spectroscopy provides information about the metal sites and
the local environment in sucient detail to often assign a
structure to a well-dened site. Vibrational spectroscopies (IR,
C
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Figure 1. (a) Compacting and sieving the support. (b) Calcination of the support in static (left) or ow conditions (right). (c) Rehydroxylation of
the support. (d) Dehydroxylation of the support (for Tdehydroxylation > 500 C quartz reactors are necessary). (e) Titration of surface hydroxyls using
MeMgBr solution in Et2O and GC quantication of released methane.
ne structure spectroscopy (EXAFS) provide information

about the oxidation state, the geometry, and the distances
between the metal and close neighbors. Though these methods
can be quite powerful, they only provide average structural
information when several sites are present.59,60 In some cases,
EPR, XPS, Auger, and Mossbauer spectroscopies can also
provide complementary information about the oxidation state
and local symmetry of MOMLn.1
In the past 20 years solid-state NMR spectroscopy (SSNMR)
has emerged as one of the most powerful characterization tools
for well-dened heterogeneous catalysts because it provides the
most detailed information on the molecular structure and
dynamics of surface sites.61,69,76 However, solid-state NMR
typically suers from an intrinsic lack of sensitivity that is
exacerbated in well-dened heterogeneous catalysts because the
surface sites are only a small fraction of the samples (few wt %).
Raman, resonance Raman) are critical to understand the

chemistry occurring at the surface.6,39,4749 For example,
monitoring a grafting reaction by IR spectroscopy shows the
consumption or interaction of MSOH with LnMX. IR
spectroscopy can be used either in transmission mode using a
self-supporting disk or in diuse reectance (DRIFT) mode
directly on powdered samples. Raman spectroscopy is
particularly useful for metal oxo surface species or surface
(MO)n rings.45,86,87 Vibrational spectroscopy also gives
specic signatures when MOMLn is put into contact
with probe molecules such as CO, CO 2 , or pyridine.4346,50,51,58 Diuse reectance spectroscopy in UV and
visible regions (DRUVvis) is used to distinguish isolated sites
from aggregates and to monitor active sites containing
adsorbing/emitting ligand.8,5257,88 X-ray adsorption near
edge spectroscopy (XANES) and extended X-ray adsorption
D
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In addition, the surface sites are often present as a distribution

of species due to dierent local environments, which leads to
signicant line broadening. Major advancements in signal
enhancements have recently been achieved with application of
polarization techniques, in particular dynamic nuclear polarization (DNP). In DNP an exogenous (organic) radical is
added to the sample in a solution that is then frozen at 100 K.
Irradiation of the EPR transition of the radical at this
temperature at the resonant NMR frequency of the experiment
leads to polarization transfer from the radical to the solvent.89,90
Cross-polarization from the solvent to the surface nuclei results
in very large signal enhancements. This technique is referred to
as Surface Enhanced NMR spectroscopy (DNPSENS).65,67,68,75,91 DNP-SENS decreases NMR experimental
time by several orders of magnitude, currently up to ca.
250 000.9294 This technique has readily been applied to a
broad range of nuclei to characterize surfaces, e.g., 13C, 15N,
17
O, 27Al, 29Si, and 119Sn.
Spectroscopy of surface species can also be accompanied by
the preparation of soluble molecular analogues. These models
are more easily characterized by solution techniques, and their
spectroscopic signatures can be compared to those of surface
species. Crystallographic parameters of molecular complexes
can be used for building models for the interpretation of XAS
data of the supported species. This approach is particularly
powerful with silica-supported systems since numerous
molecular analogues are available (see section 3.2.1.1).
Computational chemistry is a complementary tool to obtain
energetic proles that can relate to structural preferences and
particular spectroscopic signatures of surface species that may
relate to catalytic activity. Computational methods can conrm
or rule out possible structures and allow a deeper understanding of the relation between structure and reactivity.8385
Taken together, the information obtained by combining
complementary techniques in the characterization toolbox
allows for an atomic-level description of surface sites. This is an
essential step toward building structureactivity relationships
that are at the heart of rational catalyst design.
of primary particles and surface properties of the solid

according to N2 physisorption and microscopy. Metallic
utensils such as spatula should be avoided at all times to
prevent adventitious metal contamination.
The support is then subjected to calcination conditions,
heating to ca. 500 C in air to remove organic impurities.
Calcination can be carried out under static conditions in air for
small quantities of supports or under ow conditions using
synthetic air. Both static and ow calcination setups are shown
in Figure 1b. If the calcination temperature is higher than the
desired dehydroxylation temperature, a rehydroxylation step is
needed. The calcined sample is exposed to a vapor pressure of
degassed distilled/deionized water at room temperature and
further heated to the desired temperature, typically 150200
C, to promote rehydroxylation. The rehydroxylated support is
now ready for dehydroxylation. An experimental setup for this
step is shown in Figure 1c.
The dehydroxylation temperature determines the density of
surface hydroxyl groups.40 A typical dehydroxylation setup uses
a reactor tube that is 4.5 cm in diameter and ca. 50 cm in length
equipped with a tap of large aperture, as shown in Figure 1d. In
this setup the quantity of support should not exceed 510 cm3.
Using larger amounts can result in partial dehydroxylation
leading to higher than expected hydroxyl coverage. This is
probably due to problems of heat transfer or pressure drop
when large quantities of supports are used. The temperature
ramp used to reach the dehydroxylation temperature should
typically not exceed 5 C min1 to prevent sintering. This is
particularly important for mesoporous supports that can
undergo pore collapse. After the dehydroxylation temperature
is reached for an appropriate amount of time (412 h), the
reactor is cooled to room temperature under vacuum.
Dehydroxylation can preferably be performed horizontally for
better heat transfer.
IR, 34,40 thermogravimetric analyses, 95,96 solid state
NMR,67,70,73 deuterium exchange,40 titrations with organometallic reagents, 34,9799 surface silylation followed by
elemental analysis,100 and other methods were developed to
identify the type and quantity of surface hydroxyl groups on
metal oxides. Precise quantication can be performed by the
reaction of a partially dehydroxylated oxide with a Grignard
reagent and quantication of the protonated product by GC or
solution NMR. The quantication of CH4 is a three-step
procedure shown in Figure 1e. A large excess of MeMgBr in
solution in Et2O is added to a known quantity of the support
(typically 1 g) in an evacuated Schlenk ask and maintained at
room temperature for 1 h. The liquid phase is vacuum
transferred to a large (ca. 10 L) evacuated round-bottom ask.
The large size is chosen to allow quantitative transfer of all
contents from the Schlenk ask to a stable gas phase below the
vapor pressure of the solvent. Quantication of CH4 by GC
gives the OH coverage. Alternatively, the reaction of Mg(CH2Ph)2 with the oxide in C6D6 releases toluene that can be
quantied in the presence of a ferrocene as internal
standard.98,99
2.3.2. Grafting. Grafting a metal precursor onto oxide
supports requires strict anhydrous and anaerobic conditions.
This is due to the general sensitivity of many metal complexes
to air and water in solution and the increased sensitivity of
surface species supported on high surface area oxides. A basic
set of glassware designed to carry out grafting in inert
conditions using either a glovebox or a Schlenk line is shown
in Figure 2. If the molecular precursor and solvents are
2.3. Practical Aspects
Specic glassware and procedures based on Schlenk and highvacuum techniques have been developed throughout the years
to allow for easy and reproducible syntheses. These procedures
require high vacuum (105 mbar), heating, and pristine storage
capabilities. We will present an overview of relevant
experimental setups and processes.
2.3.1. Preparation and Characterization of the
Supports (Calcination, Dehydroxylation, and Passivation). Supports used in SOMC can be prepared and
characterized using similar procedures. It is important to
evaluate the structure of the support after each step of the
preparation process because some oxides can readily change
phase or sinter in the presence of water when heated. Oxides
are typically purchased or prepared by solgel or alternative
methods as ne powders. A trick of the trade is to agglomerate
the ne powder into larger, easier to lter, particles by wetting
with water followed by slow evaporation at 120 C in an oven
solely used for inorganic solids. For silica and alumina, the
typical compaction steps are summarized in Figure 1a. A slurry
of the oxide powder in distilled water is dried at ca. 120 C for
several days in an oven, resulting in the formation of large
agglomerates. These agglomerates are sieved to select particles
of 250400 m in size. This treatment does not change the size
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Figure 2. (a) Grafting in a Schlenk ask. (b) Grafting in a double-Schlenk ask. (c) Grafting by sublimation of the precursor using break-seal
technique.
the two arms of the ask, as shown in Figure 2b. A solution of

the organometallic reagent is placed in one side of the doubleSchlenk while the support is added to the other side. The
solution is degassed by a freezepumpthaw cycle, added to
the support through the lter, and the resulting suspension is
slowly stirred. After the reaction, the supernatant is ltered into
the other arm of the double-Schlenk. Avoiding the solid to go
in contact with the glass lter is advised. To wash the
functionalized oxide the solvent is transferred back into the
other chamber of the double-Schlenk via vacuum distillation.
The ltrate is then separated from the solids as in the previous
step. This washing step is repeated 23 times depending on the
solubility of the reactant and byproducts. The ltrate is
collected and the product of the grafting reaction is quantied
by solution NMR using an internal standard.
Volatile molecular precursors can be grafted in the gas phase
by sublimation of the compound onto the support using a
break-seal tube connected to a reactor, shown in Figure 2c. In
this case the excess reagent is sublimed back in the side tube,
which can be sealed using a ame.
For preliminary studies the steps described above can be
performed on pressed pellet (self-supporting disk) for direct
monitoring of the surface chemistry by IR spectroscopy as
compatible with their use in glovebox, grafting can be

conveniently carried out in a Schlenk ask (Figure 2a). In
this case, a solution of the molecular precursor is added to a
slurry of the support in the same solvent. Stirring should be
performed carefully since vigorous stirring tends to break apart
the agglomerates to form a very ne powder. While a 3 h
grafting time is typically sucient to complete the reaction, it is
best to monitor the consumption of surface hydroxyls by
spectroscopic methods such as IR. After the reaction the
supernatant is ltered away from the solid. The solid is washed
with fresh solvent and the supernatant again removed. This
rinsing step is repeated 23 times to remove any unreacted
molecular precursor and the product of the grafting reaction
(HX in Scheme 1). The combined ltrates contain the
coproduct of the grafting reaction that is typically quantied
by solution NMR using an internal standard. The functionalized oxide is dried on a high vacuum line prior to long-term
storage in a glovebox. As mentioned above, the quantity and
type of product(s) evolved during grafting, metal loading, and
C, H, N elemental analyses give the stoichiometry of the
grafting reaction (often referred to as mass balance analysis).
Outside of a glovebox the grafting reaction is carried out in a
double-Schlenk ask containing a sintered glass lter between
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Figure 3. Calcination, dehydroxylation and grafting on a pressed pellet of a support.
the, now MSOH depleted, oxide surface. The reaction of the

site-isolated MSOH with molecular precursors forms welldened surface species, which can then be post-treated to
modify their environment. Below we describe this approach to
form well-dened surface species on partially dehydroxylated
silica (section 3.2.1), alumina (section 3.2.2), and silica
alumina (section 3.2.3). Section 3.2.4 discusses grafting on
other oxide supports. In section 3.3 we describe post-treatment
strategies to modify grafted species in order to probe surface
site structure or to generate new surface sites.
shown in Figure 3. After pressing a sample of the support in air

the pellet is placed in a holder designed to slide up and down a
reactor. The head of the reactor contains IR transparent
windows (CaF2, KBr, ZnSe, etc.) that allow acquisition of the
spectra. The calcination and dehydroxylation are carried out in
the reactor. After dehydroxylation the reactor is taken into a
glovebox, and the pellet is submerged into a solution containing
the molecular complex. Washing is accomplished by submerging the pellet in fresh solvent. If the reagent is volatile it can
also be distilled/sublimed onto the pellet.
2.3.3. Storage and Handling. Because of their dispersion
on a high surface area supports, most grafted complexes show
an increased sensitivity to contaminants by comparison to their
homogeneous analogues. For that reason, supported materials
are best stored in ground glass storage tubes kept in solventfree gloveboxes.
3.2. Structure of Surface Species Resulting from Grafting of

the Molecular Precursors
3.2.1. Silica-Supported Well-Dened Metal Sites.

3.2.1.1. General Considerations on Silica. Silica is typically
an amorphous material with relatively high surface areas
between 50 and 1000 m2 g1.34,40,42 Quartz and cristobalite
are crystalline, but the very low surface area of these materials
(2.6 m2 g1 and 2.1 m2 g1, respectively)101 limits the number
of surface sites per unit mass that restricts their application as
supports for heterogeneous catalysts. The texture and shape of
amorphous silica depends mainly on the preparation method.
Flame pyrolysis of SiCl4 and H2/O2 above 1000 C results in
high purity, nonporous silica with moderate to large surface
area (50380 m2 g1).102104 Mesostructured materials such as
MCM41 and SBA15 are prepared using solgel methods in the
presence of a surfactant as a template to form large and ordered
mesopores.105 These materials have surface areas up to 1000 m2
g1. Note that treatment of mesoporous materials at high
temperatures, above 500700 C, may result in the collapse of
the porous network.42
The bulk of silica is composed of tetrahedral SiO4 units
connected to each other to form siloxane rings of various sizes
3. DESCRIPTION OF THE SURFACE CHEMISTRY ON

OXIDES
3.1. General Concepts, Strategy, and Methods
To restate, the key concept in SOMC is treating oxide surfaces

as an isolated X-type anionic ligand as shown in Scheme 1. The
controlled structure of the surface species, deduced from
spectroscopic studies, and catalytic behavior allow building a
structureactivity relationship and thereby more rational
development of heterogeneous catalysts. Oxide supports are
terminated by MSOMS, MSOH, and in some cases MS
OH2 functionalities. Thermal treatment removes adsorbed
water and condenses nearby MSOH sites to form more water
and MSOMS on the oxide surface. This process reduces the
overall density of MSOH groups that can be functionalized on
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Figure 4. (a) Types of silanols. (b) Infrared spectra of Aerosil-200 partially dehydroxylated at 200 and 700 C (SiO2200 and SiO2700). (c) Siloxane
rings. (d) Eect of temperature on surface OH density.
ranging from exible 12-membered rings to strained 4membered rings (Figure 4). The silica surface exposes siloxane
rings/bridges and is also terminated with dierent types of
silanols (Figure 4a). Geminal and isolated silanols are present
even at very high thermal treatment temperatures (>700 C)
and are readily observable using IR spectroscopy.34,106 Vicinal
silanols are two silanol sites in close proximity on the surface
that form hydrogen bonds with one another.40,42 Vicinal
silanols appear in the IR spectrum as a broad red-shifted band
centered at 3650 cm1. Treating silica at temperatures above
150 C under vacuum or in a stream of (inert) gas results in
desorption of physisorbed water. Above this temperature vicinal
silanols begin to condense to form siloxane bridges liberating
more water. Using fumed Aerosil-200 (200 m2 g1) as an
example, the decrease of surface silanol concentration is nearly
exponential with increasing temperature (Figure 4d). The
SiOH density decreases from ca. 3 OH nm2 to ca. 0.8 OH
nm2 for Aerosil-200 partially dehydroxylated at 200 and 700
C. In silica partially dehydroxylated at 700 C (SiO2700)
mostly isolated silanols are present, but 510% of the silanols
are also geminal.70 As the dehydroxylation temperature
increases more, strained siloxane bridges, such as 4-membered
ring siloxanes, are formed.
Cluster and periodic models of the silica surface have been
reported.107 The cluster approach has been used extensively to
model isolated geminal and vicinal silanols, and the reactivity of
these sites with organometallic complexes. Siloxane cages with
dierent SiO rings sizes are of common use in the modeling
of silica surfaces. Figure 5a shows typical siloxane cages used in
the modeling of isolated silanols, whereas Figure 5b shows a
typical model for a geminal silanol.
Several periodic models have been also proposed for the
silica surface. A periodic silica surface containing 26 SiO2 units
was cleaved from an amorphous silica bulk structure108 and
terminated with OH group,109 the nal surface containing 5.8
Figure 5. (a) Typical cluster models of SiO2 for isolated silanols with
dierent ring cages and (b) cluster model of a geminal silanol. (c) Top
and side views of the amorphous model with OH coverage equal to 1.5
OH nm2 from ref 110. (d) A crystalline models based on the (111)
surface of -cristoballite with OH coverage equal to 1.4 OH nm2
from ref 112.
SiOH nm2. An alternative amorphous silica surface model

with a SiOH nm2 coverage of 7.2 OH nm2 was also
constructed by annealing the structure of bulk -cristoballite at
very high temperatures using molecular dynamics.110 Removal
of water molecules by condensing adjacent silanol pairs gave a
surface containing silanol densities as low as 1.5 OH nm2. The
simulated IR spectrum of the model surface containing 4.5 OH
nm2 was in good agreement with experimental spectra. Other
periodic models based on -cristobalite were also reported,
which closely match experimental data.111,112 A completely
dehydroxylated periodic model originating from -cristobalite
contains strained 4-membered SiO rings in the surface. These
rings can be observed in the IR transparent window around 900
cm1.113
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3.2.1.2. Grafting Molecular Precursors on Silica and

Resulting Surface Species. Generalities. SiO2700 contains
mostly isolated silanols and low amount of strained siloxane
bridges70 and is ideal for obtaining monografted (monosiloxy)
surface species. The reaction of SiOH with a generic
LnMXx is shown in Scheme 2a. Most of the silica-supported
we also provide a summary of characterization methods for

each well-dened structure. Designations for the supports in
the tables are as follows: SG refers to any kind of silica gel,
relevant details are given in parentheses in each case. The most
commonly used Aerosil-200 (Degussa, 200 m2 g1) is
designated as AS. Less common Aerosil silicas with surface
areas of 300 and 380 m2 g1 are listed as AS300 and AS380,
respectively.
Homoleptic Alkyl Complexes. Homoleptic complexes of
the group 46 transition metals of the general formula MRx
react with SiOH to form grafted species and RH. The two
driving forces for this reaction are the release of RH and the
formation of a strong MO bond. Early reports of this reaction
date to the 1970s using mainly allyl24,25,115119 or methyl
complexes of group 4 and 6 metals.120,121 More recent studies
have focused on methyl, neopentyl, neosilyl, and benzyl
derivatives. Table 2a summarizes the reaction of homoleptic
group 4 alkyl complexes, complexes of group 5 and 6, and later
transition-metal alkyl complexes, respectively. The reaction of
MRx with SiO2700 forms the monografted (SiO)MRx1
(Scheme 2a, X = R). In contrast, the reaction of MRx and
silica partially dehydroxylated at lower temperatures, such as
SiO2200, have an average structure consistent with the formula
(SiO)2MRx2 (Scheme 2b, X = R). However, current
spectroscopic methods are rarely sensitive enough to
distinguish between (SiO)MRx1, (SiO)2MRx2, and (
SiO)3MRx3 for this class of compounds, in particular since bisgrafted species are associated with a distribution of species that
leads to broader spectral line width. With silica partially
dehydroxylated at intermediate temperatures (300500 C),
the reaction stoichiometry indicates that mixtures of (
SiO)MRx1 and (SiO)2MRx2 are obtained. Grafting also
occurs with late-transition metal complexes M(allyl)2 (M = Ni,
Pd, Pt),122125 M(allyl)3 (M = Rh),126,127 and Fe(aryl)2 (aryl =
mesityl or 2,4,6-tritertiobutylphenyl).128 In contrast, [Au(Mes)]5 does not react with surface silanols leading to
physisorbed complex.129 The most recent examples are listed
in Table 2a.
Homoleptic and Related Amide Complexes. Metal amide
complexes are widely available for most transition metals.154
The reactivity of metal amides with partially dehydroxylated
silica is similar to homoleptic alkyl complexes. The polarized
MN bond in M(NR2)n reacts with SiOH to form (
SiO)M(NR2)n1 and HNR2 (Scheme 2, X = NR2). Tables 2b
and 2c give examples of grafting of d-block metal-amides and
group 3/lanthanide amides on silica, respectively.
The reaction of Ti(NEt2)4 with SiO2500 forms (
SiO)Ti(NEt2)3 and HNEt2 (Table 2b, entry 1).155 Zr(NMe2)4
reacts with SiO2700 in a similar fashion, though the
intermediate (SiO)Zr(NMe2)3 undergoes -H abstraction
to form Zr-3m shown in Scheme 3 and Table 2b (entry 6).156
The analogous reaction with (SiO)2Ti(NR2)2 only occurs at
elevated temperature (60 C).157 W2(NMe3)6 contains a
tungstentungsten triple bond that remains intact upon
grafting onto SiO2700 to form (SiO)W(NMe2)2(W(NMe2)3) (Table 2b, entry 8).158
Silyl amide derivatives M(N(SiMenH3n)2)x is perhaps the
most studied class of metal amide complexes. The reaction of
M(N(SiMenH3n)2)x with SiOH forms (SiO)M(N(SiMenH3n)2)x-1 and HN(SiMenH3n)2. In this case HN(SiMenH3n)2 further reacts with SiOH to form (
SiO)SiMenH3n (Scheme 4).18 This competitive passivation
results in lower loadings that one would expect based on the
Scheme 2. Grafting of MLnXx Molecular Precursor on (a)

SiO2700 and (b) SiO2200 and (c) Examples of Molecular
Silanols Used To Prepare Molecular Analogues of Surface
Species
species described below follow this general reaction path

involving proton transfer to the MX group to form (
SiO)MLnXx1 surface species after the release of HX. There are,
however, several exceptions to this rule, and we will discuss
these below when appropriate. Silica prepared at lower
dehydroxylation temperatures contains vicinal silanols, and
bis-grafted (bis-siloxy) surface complexes are preferentially
obtained.114 The reaction of metal complexes with SiO2200 or
SiO2300 typically leads to a reaction stoichiometry (elemental
analysis and mass balance) consistent with the formation of bisgrafted species (Scheme 2b). However, it is very important to
obtain spectroscopic evidence for such species as stoichiometry
can be misleading since it only provides an average structure
(vide infra). In addition, characterization of the surface species
can be complemented by preparing molecular analogues using
molecular silanols (Scheme 2c).7782
In this section we provide a comprehensive list of welldened lanthanide, group 3, and transition-metal complexes
supported on partially dehydroxylated silica. The sections and
associated tables are divided according to the types of ligands
found in the molecular precursors and by metal. In the tables
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Table 2. Well-Dened Silica-Supported Surface Complexes
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AB
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AC
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AD
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AE
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AF
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AG
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AH
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AI
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AJ
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Estimated value.
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Scheme 3. Grafting of Zr(NMe2)4 on SiO2700
Scheme 4. (a) Grafting of Bis(trimethyl)silylamide Complexes on Silica and (b) Possible Surface Species with Lanthanide and
Group 3 (Ln) Metal Complexes
Scheme 5. Grafting and Further Evolution of [Ti(OiPr)4]2 on SiO2500
dimeric [Ta(OMe)5]2 reacts with SiO2700 to form the

monomeric (SiO)Ta(OMe)4 (Table 2d, entry 4).186 In
[Cu(OtBu)]4 grafting, the tetrameric structure is conserved
(Table 2d, entry 6),187189 and a tungsten dimer is intact in the
reaction of [W(OEt)5]2 with SiO2700. In the latter case bis- and
tris-grafted species are obtained because of the reaction of
adjacent siloxane bridges promoted by the presence of W
(Table 2d, entry 5).190
A large number of complexes containing the OSi(OtBu)3
ligand react with silica to form well-dened surface species
(Table 2e). Grafting typically displaces a siloxy ligand, though
in a few cases a OtBu in the siloxide reacts with surface
silanols (Table 2e, entries 25). Complexes containing the
(tBuO)2Si(O)2 ligand react with silica by selective displacement
of OtBu groups (Table 2e, entry 6). M[OSi(OtBu)3]n
complexes react with partially dehydroxylated silica to form
well-dened surface species of Ti, Cr, Fe, Cu, and Zn. In the
case of Cr(II) a dimeric siloxide remains dimeric when
supported on silica (Table 2e, entry 10). THF-containing
siloxides have similar reactivity with partially dehydroxylated
silica as THF-free siloxide complexes. The reaction of related
Ti(OGeiPr3)4 with partially dehydroxylated silica occurs
exclusively at the TiO bond to form (SiO)Ti(OGeiPr3)3
(Table 2e, entry 7).191 Grafting of molecular complexes
containing both alkoxy and siloxy ligands is not selective,
even if displacement of the siloxy ligand is typically favored
(Table 2e, entries 35 and 8).
Metal Chlorides. MCln derivatives react with partially
dehydroxylated silica to form (SiO)MCln1 and HCl. These
structures are summarized in Table 2f. Compared to MRx,
quantity of surface silanols present on the partially dehydroxylated silica support.

When M(N(SiMenH3n)2)x contains bridging ligands the
grafting reaction typically forms the corresponding mononuclear grafted complex (Table 2c). In the specic case of
[Ag(N(SiMe3)2)]4 the initial nuclearity was preserved (Table
2c, entry 10).159 With heteroleptic complexes having amide and
silylamide ligands, the structures of the nal surface species are
probably complex due to the competitive reactivity of amide
and silylamide toward surface silanols (Table 2c, entry 1).
Molecules with coordinated solvents generally form the
corresponding solvent adducts on the surface (Table 2c, entries
5 and 8). Ln(N(SiMenH3n)2)3 complexes follow qualitatively
similar trends, these species are shown in Table 2c, entries
1317. As for homoleptic MRx complexes discussed above,
silica dehydroxylated at lower temperatures reacts with
M(NR2)n complexes to form mixtures of surface species with
greater fraction of bis-grafted species.
Homoleptic Alkoxide Complexes. Metal alkoxide complexes react with partially dehydroxylated silica in similar
fashion as described for alkyl and amide complexes. SiO2700
gives primarily monografted products, and silicas with higher
hydroxyl content give mixtures of surface species (Table 2d,
entry 1).
The trends to conserve or disrupt multimeric alkoxide
structures are dependent on the metal. The reaction of dimeric
[Ti(OiPr)4]2 with SiO2500 is reported to give Ti2-6m, which
loses one OiPr ligand through a -abstraction process
generating propene and the 2-O bridged species Ti2-6m
(Scheme 5 and Table 2d, entries 2, 3).155,185 However, the
AL
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(tBuO)3SiO. This is also supported by the dierence in

buried volume between a surface siloxy in cristobalite and
OSi(OtBu)3.211 In contrast, when Rh-4, Rh-5, and Rh-6 are
reacted with SiO2350 the resulting mononuclear Rh-species are
stabilized by an additional nearby silanol (Table 2h, entries 3
5).
The reaction of (COD)PtX2 with partially dehydroxylated
silica depends on the nature of X ligand. With (COD)PtCl2 or
(COD)PtMe2 very little grafting occurs. However, complexes
containing amides or siloxides, such as (COD)Pt(N(SiMe3)2)
(Me) or (COD)Pt(OSi(OtBu)3)Me, react cleanly with SiO2 to
form monografted PtMe surface species with a selective
displacement of the O- and N-bound ligand (Table 2h, entries
813). [Re(CO)3OH]4 grafts on silica with liberation of H2O
as shown in Scheme 7.212
M(NR2)n, and M(OR)n, fewer MCln salts have been supported

on silica to form well-dened sites. This is probably due to
limitations in spectroscopic methods, which are major hurdles
to support the structure of the proposed surface species. The
presence of THF or Et2O in the coordination sphere of the
metal chloride does not seem to aect grafting.
Heteroleptic Complexes with Various Monoanionic
Ligands. From a purely thermodynamic point of view, the
reaction of MXx with dehydroxylated silica is most favorable
when X = alkyl and less favorable when X = OR or Cl,
particularly for early transition metals. From a kinetic
perspective, in the specic case comparing the reaction of
Zr(CH2tBu)4 and Zr(OtBu)4 with oxide supports, grafting of
alkoxide (X = OR) is much faster than alkyl (X = CH2R). This
may be due to faster proton transfer from the surface hydroxyl
groups to the lone pair on oxygen in ZrOR. This two step
grafting process is evidently faster than direct proton transfer of
the surface hydroxyl groups to ZrR, involving a three center
two electron intermediate (Scheme 6).207,208 Despite this
Scheme 7. Grafting [Re(CO)3OH]4 onto SiO2
Scheme 6. Interaction of Zr(OtBu)4 and Zr(CH2tBu)4 with

Surface Hydroxyl Groups of Silica and Alumina
Metal Cyclopentadienyl Complexes. Grafting cyclopentadienyl complexes, CpyM(X)xLn (Cp = C5H5 or C5Me5) on
partially dehydroxylated silica leads to protonolysis of the X
ligand. These results are summarized in Table 2i. Note that for
homoleptic M(Cp)n complexes grafting on silica forms (
SiO)M(Cp)x1 with the release of CpH (Table 2i, entries 3, 4,
8, 9).
Metal Aluminate Complexes. The reaction of lanthanide
amides with AlMe3 species forms Ln(AlR4)3 complexes.229236
These complexes react with partially dehydroxylated silica to
give a mixture of surface species. In general, Ln(AlR4)3 is
proposed to react with silica to form mono- and bis-grafted
lanthanide species and alkylaluminum grafted species shown in
Scheme 8.237,238 Grafting of some other aluminate-supported
lanthanide derivatives was also studied and shows similar results
(Table 2j).
kinetic dierence in reactivity, the thermodynamic product is

normally obtained when grafting heteroleptic complexes. There
are only a few examples, shown in Table 2g, of grafting felement complexes containing dierent types of anionic ligands.
With metal complexes containing alkyl and aryloxide ligands,
the alkyl group is displaced. This behavior is expected based on
thermodynamic considerations because in these cases the
SiOM bond is stronger than the MR bond. Similar
observations were made when alkyl and halide ligands were
present in the same compound.
Metal Complexes Containing Neutral and Anionic
Ligands. Metal complexes containing both anionic (X) and
neutral (L) ligands typically react with partially dehydroxylated
silica by protonolysis of the anionic ligands with the neutral
ligand remaining bound to the surface complexes.
Diolen Metal Complexes and Other C-Centered Ligands.
Dinuclear complexes like [(COD)M(OR)]2 (M = Rh and Ir)
containing bridging alkoxide ligands react cleanly with SiO2700
to generate monografted species [(COD)2M2(OSi(OtBu)3)(OSi)] while maintaining the dinuclear structure (Table 2h,
entries 12 and 67). EXAFS analysis of [(COD)M(OSi(OtBu)3)]2 and [(COD)2M2(OSi(OtBu)3)(OSi)] showed
that the surface complex has a much shorter MO and MSi
distances than [(COD)M(OSi(OtBu)3)]2. This result indicates
that surface siloxy ligand, SiO, is a smaller ligand than
Scheme 8. Grafting Nd(AlMe4)3 onto Silica
Metal Complexes Containing N- and P-Donor Ligands.

Complexes containing N- or P-donor ligands react in a similar
fashion with partially dehydroxylated silica. In the family of
Pd(X)(Y)(PR3)2 in which X = Me and Y = OTf, Cl, NO3 the
methyl ligand is selectively replaced by surface siloxy (Tables 2k
and 2l).239 In some cases cationic surface species were
claimed.239
Metal Complexes Bearing O- and S-Donor Ligands.
Acetylacetonate and Carbamate Derivatives. Despite the large
number of metal acetylacetonate derivatives, only few examples
of well-dened silica-supported species have been reported.
This is probably related to the low reactivity (and solubility) of
most of these acac derivatives. Y(fod)3,178 Zr(acac)4,253 and
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Scheme 9. Grafting (a) Ta(CHtBu)(CH2tBu)3, (b) Re(

CtBu)(CHtBu)(CH2tBu)2, and (c) Os(
CHtBu)2(CH2tBu)2 on SiO2700
Ir(acac)3254 generate the corresponding grafted species by

protonolysis of the acac ligand to form monografted surface
species (Table 2m, entries 13). Though Me2Au(acac) does
not react with silica,255 the carbamate Au-4 does form Au-4m
(Table 2m, entry 5).256
O- and S-Calixarene-Capped Metal Complexes. Calixarenes
have been mainly used as tri- or tetra-anionic O-based ligands
for group 4, 5, or 6 metal complexes.257259 The reaction of
calixarene complexes with partially dehydroxylated silica results
in displacement of an anionic ligands, usually Cl or OR. This
forms the calixarene-capped silica-supported metal complexes
shown in Table 2n. The Ta calixarene complexes Ta-7/8 were
grafted onto SiO2300 to form Ta-7b/8b, containing a
protonated arm of the calixarene ligand and two surface siloxy
groups (Table 2n, entries 1011).
Metal Oxo and Imido Complexes with Monoanionic
Ligands. Early transition metal imido and oxo derivatives
grafted on silica are summarized in Table 2o and Table 2p. The
oxo and imido ligands usually remain intact upon grafting onto
silica. However, in certain cases characteristic NH IR
vibrations267,268 and NMR signatures268 of an amido ligand
are present after grafting of imido complexes, indicating that
protonation of the imido ligand occurs (Table 2o, entries 12).
Currently available data, including 17O NMR studies of 17Olabeled surface oxo complexes,74,269 does not show evidence of
the oxo ligand being involved in this transformation. As found
in homoleptic complexes, oxo and imido molecular precursors
generally react with SiO2700 to form monografted complexes,
but mixtures form on silica dehydroxylated at lower temperatures. In contrast, molybdenum bis-imides react with SiO2200
and SiO2500 to generate solely monografted products as the
sole surface species (Table 2o, entries 4 and 5).
There is currently no quantitative model on the relative
reactivity of X ligands in heteroleptic oxo or imido complexes.
While V(NtBu)(CH2tBu)2(OtBu) grafts on SiO2500 to form
(SiO)V(NtBu)(CH2tBu)(OtBu) (Table 2o, entry 2),267
W(O)(CH2tBu)3Cl reacts with SiO2700 by selective WCl
bond cleavage resulting in the formation of (SiO)W(
O)(CH2tBu)3 as a sole product (Table 2p, entry 17).74
Among the most extensively studied is the reaction of VOCl3
with silica.270276 Monografted species are formed on highly
dehydroxylated silica (Tdehydrox > 500 C).271276 At lower
dehydroxylation temperatures there is no consensus on the
structure of the dominant surface species.
Metal Alkylidene Complexes. The reaction of metal
alkylidene complexes with partially dehydroxylated silica
typically results in the formation of well-dened silicasupported metal alkylidenes (Table 2q2s and Scheme
9a). 288 For example, the reaction of Ta(CHtBu)
(CH 2 tBu) 3 with SiO 2700 yields (SiO)Ta(CHtBu)
(CH2tBu)2. In this case the alkylidene ligand participates in
the grafting step (Scheme 9a). The reaction of Ta(CHtBu)
(CH2tBu)3 with partially dehydroxylated deuterated silica forms
(SiO)Ta(CDtBu)(CH2tBu)2 and (SiO)Ta(CHtBu)
(CHDtBu)(CH2tBu) that incorporate deuterium. This result
indicates that (SiO)Ta(CHDtBu)(CH2tBu)3 forms transiently and undergoes H-transfer to form the nal surface
species.225,289,290 Similar results were obtained for the grafting
of Re(CtBu)(CHtBu)(CH2tBu)2 (Scheme 9b and Table
2q, entry 5).291 The extreme scenario is the reaction of
Cp2Ta(CH2)Me with SiO2450, which yields (SiO)TaCp2Me2. In this case, SiOH quantitatively protonates
the TaCH2 group (Table 2q, entry 4).226
In sharp contrast, the reaction of Os(CHtBu)2(CH2tBu)2

with SiO2700 yields the alkylidyne complex (SiO)Os(
CtBu)(CH2tBu)2 (Scheme 9c, Table 2q, entry 6).292 (
SiO)Os(CtBu)(CH2tBu)2 forms by reaction of the silanol
with Os(CtBu)(CH2tBu)3 as a result of isomerization of
Os(CHtBu)2(CH2tBu)2 by -H transfer upon coordination;
this forms (SiOH)Os(CHtBu)(CH2tBu)3 that subsequently releases 2,2-dimethylpropane by -H abstraction.
DFT studies show that (SiO)Os(CtBu)(CH2tBu)2 adopts
a buttery geometry, which is favored over a tetrahedral
geometry due to the presence of a weak siloxy ligand and the
Os in d2 conguration.
Grafting imido alkylidenes of the type M(NAr)(
CHR)(X)2 (M = Mo or W, X = CH2R, OR or NR2) onto
partially dehydroxylated silica yields the corresponding surface
complexes in which one X ligand is replaced by a siloxy surface
group (Table 2r). Protonation of the alkylidene ligand to form
(SiO)M(NAr)(CH2R)(X)2 is observed in some cases. In
contrast to Ta(CHtBu)(CH2tBu)3 or Re(CtBu)(
CHtBu)(CH2tBu)2, (SiO)M(NAr)(CH2R)(X)2 is stable
and does not form (SiO)M(NAr)(CHR)(X) upon
heating up to 150 C. The formation of (SiO)M(
NAr)(CH2R)(X)2 can be suppressed by lowering the grafting
temperature. For example, grafting W(NAr)(CHtBu)(OtBu)2 at 40 C in place of room temperature forms ca. 30%
less (SiO)W(NAr)(CH2R)(OtBu)2 than if the reaction is
carried out at room temperature.211
The reaction of SiO2200 and W(NAr)(CHtBu)
(CH2tBu)2 forms ca. 2 equiv of 2,2-dimethylpropane per W
on the surface, in agreement with the formation of bis-grafted
(SiO)2W(NAr)(CHtBu). Analysis of this material by
solid-state NMR showed that several products were present on
the silica surface, as shown in Scheme 10.293 This reaction
forms the monografted (SiO)W(NAr)(CHtBu)(CH2tBu), bis-grafted (SiO)2W(NAr)(CHtBu), the
bis-grafted protonated alkylidene (SiO) 2 W(NAr)(CH2tBu)2 species along with other unidentied species
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Scheme 10. Identied Species upon Grafting of W(

NAr)(CHtBu)(CH2tBu)2 on SiO2200
Scheme 12. Grafting Ruthenium Alkylidene Complexes on

SiO2200
(Scheme 10). This result shows the degree of complexity that

can be encountered when using silica dehydroxylated at lower
temperatures where high concentrations of vicinal silanols are
present.
W(O)(CHR)(OAr)2 (OAr = 2,6-dimesitylaryloxide
(HMTO) or 2,6-diadamantylaryloxide (dAdPO)) behaves
similarly in the presence of partially dehydroxylated silica to
form supported oxo alkylidene surface species (Table 2s).
Protonation of the alkylidene does occur, but is dependent also
on the size of the OAr ligand. For small W(O)(
CHR)(OHMT)2 an 80:20 mixture of (SiO)W(O)(
CHR)(OAr) and (SiO)W(O)(CH2R)(OAr)2 was obtained. The larger W(O)(CHR)(OdAdP)2 gives a 90:10
ratio of the grafted alkylidene complex.
Solid-state NMR has proven particularly powerful in
determining the structure and dynamics of alkylidene species
supported on silica. The 1H MAS and 13C CP MAS spectrum
of (SiO)Re(CtBu)(CHR)(CH2R) contains signals for
both syn and anti isomers (Scheme 11).294 J-resolved solid state
yields (SiO)M(E)(X)2. As in the other cases mentioned

before, reacting M(E)(X)3 with SiO2200 forms mixtures of
mono- and bis-grafted species. One exception to this reactivity
pattern in the M(E)(X)3 family is Mo(N)(CH2tBu)3,
which reacts with SiO2700 to form (SiO)2Mo(NH)(CH2tBu)3 by protonation of the nitrido ligand (Scheme 13
Scheme 13. Grafting of Mo(N)(CH2tBu)3 on SiO2700
and Table 2u, entry 1).319,320 Heteroleptic alkylidyne

complexes containing alkyl or aryloxy ligands react with
partially dehydroxylated silica to give surface species containing
intact alkylidyne ligands (Table 2t).
3.2.1.3. Modication of Silica Surfaces with Main Group
Organometallics. In this section we provide a selection of
reactions of main group organometallics with silica because of
their relevance as cocatalysts (see section 4).
Mg(CH2tBu)2(dioxane) reacts with SiO2400 to give grafted
magnesium surface species (Scheme 14a).327 With silica
dehydroxylated at 620 C SiR fragments are also formed
through the opening of siloxane bridges (Scheme 14b).328
Scheme 11. syn and anti Isomers of (SiO)Re(CtBu)(

CHR)(CH2R)
Scheme 14. Reaction of Grignard Reagents with (a) Silanol

Groups and (b) Siloxane Rings
NMR spectroscopy shows that the J(CH) coupling constant

associated with the alkylidene CH bonds were 109 and 159
Hz, consistent with the assignment to syn and anti isomers,
respectively. The low JCH obtained for the major syn isomer is
consistent with the presence of an -agostic interaction, which
is known for similar isoelectronic molecular complexes.295,296
Isoelectronic silica-supported Mo- and W-imido as well as Woxo alkylidene complexes always form the syn isomer as the
only detectable product. In addition, NMR studies of a large
family of silica supported Ta, Mo, W, and Re alkylidene species
revealed that Ta and Re are dynamic species (e.g., rotation
around OM bond), while the Mo- and W-imido species are
static62 due to the interaction of the aromatic ring with the
surface, which is also evidenced by IR spectroscopy.297
Silica-supported Ru-alkylidene chemistry is considerably less
developed. The reaction of Ru-siloxy-alkylidenes Ru-4 or Ru-5
with SiO2200 forms well-dened mono- and bis-grafed species
according to EA and SSNMR study of 13C labeled complexes.
In this case the bis-grafted species is the major product of the
grafting reaction (Scheme 12).298
Metal Alkylidyne and Nitrido Complexes. The reaction of
metalalkylidyne and metal-nitrido complexes is summarized
in Table 2t and 2u. The reaction of M(E)(X)3 (M = Mo or
W, E = CtBu or N and X = CH2tBu, NR2 or OR) with SiO2700
The reaction of alkylaluminums with high surface area

mesoporous SBA15500 yields a complex mixture of surface
species. For example, the reaction of AlEt3 with SiO2700 forms
a mixture of dinuclear alkylaluminum species and tetrahedral
aluminum sites that do not contain alkyl fragments according to
27
Al MAS NMR spectroscopy. The formation of these
tetrahedral sites, mono-, bis-, and tris-alkylsilicon surface
species, indicate that siloxane bridges are involved in the
grafting process and show the complexity of grafting reactions
of alkylaluminums onto silica surfaces (Scheme 15a).71
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SBA15500 forms a complex mixture of aluminum species

involving protonolysis of AlEt groups and alkyl-transfer to the
silica surface (Scheme 17).333335 In this case most alkyl
aluminum species contain a bridging 2-Cl-ligand.
Scheme 15. Reaction of (a) AlEt3 and (b) GaMe3 with

Dehydroxylated Silica
Scheme 17. Reaction of [Et2AlCl]2 with SBA15500
The reaction of B(C6F5)3 with partially dehydroxylated silica

was reported to give an active cocatalyst for the polymerization
of olens.336340 However, this reaction leads to hydrogenbonded surface species (Scheme 18a).341 In the presence of
Tricoordinate (SiO)AlR2, which would result from grafting

monomeric AlEt3 onto isolated silanols was not observed under
these conditions. Similar dimeric species were also formed
when GaMe3 was grafted onto partially dehydroxylated silica
(Scheme 15b).329
The reaction of AliBu3, which is monomeric in solution, and
SBA15500 leads to even more complex surface chemistry than
encountered in the grafting of AlEt3 onto partially dehydroxylated silica. In this case the bis-grafted dimeric (
SiO)4(AliBu)2 surface species is the sole alkylaluminum
containing species on the surface. Signicant amounts of
tetrahedral aluminum and dimeric aluminum sites lacking alkyl
fragments as well as alkylsilicon groups are also formed, shown
in Scheme 16a.330 This behavior is likely due to the higher
Scheme 18. (a) Absorption of B(C6F5)3 onto Silica to Form

Lewis Acid/Base Adducts; (b) Reaction of B(C6F5)3
Adsorbed on Silica and NEt2Ph to form [Et2NPh][(
SiO)B(C6F5)3]; and (c) Grafting B(C6F5)3 onto Silica in the
Presence of Water to Form (SiO)B(C6F5)2
Scheme 16. Grafting AliBu3 on (a) SBA15500 and (b)

SBA15700
amine bases, such as Et2NPh, these hydrogen-bonded silanols

react to form [Et 2 NHPh][(SiO)B(C 6 F 5 ) 3 ] ion-pairs
(Scheme 18b).342,343 However, the reaction of B(C6F5)3 with
partially dehydroxylated silica showed that grafting reactions
only occur in the presence of trace water.344 This reaction
forms the (SiO)B(C6F5)2 surface species (Scheme 18c) in
which the two borane units are in close proximity.
3.2.2. Alumina-Supported Metal Complexes.
3.2.2.1. General Consideration on Alumina. Alumina(s) has
a more complex surface chemistry than silica because of the
greater variety of surface functionalities and types of allotropes.
This oxide exists as pure phases or mixtures of , , , , and
alumina.345,346 -Alumina has low surface area (110 m2 g1)
and is mainly used for the preparation of reforming catalysts
because it is stable above 1000 C. Alumina contains a mixture
of interconnected tetrahedral AlO4 and octahedral AlO6 units.
The amount of tetrahedral aluminum decreases in the order of
(50%) to (37%) to (25%) to (0%).347353 -Alumina
can be obtained with relatively large surface areas (ca. 200 m2
g1) and is kinetically stable up to ca. 700 C when treated
under vacuum for 412 h.354 Above this temperature oxygen
reactivity of monomeric AliBu3 in comparison to dimeric AlEt3.

Although when SBA15700 is used as a support grafting
AliBu3331 or AliBu3Et2O332 leads to the sole surface products:
(SiO)2AliBu or (SiO)2AliBuEt2O, respectively. The
reaction was shown to involve siloxane bridge opening via
either alkyl or -H transfer, resulting in the formation of Si
iBu and SiH coproducts (Scheme 16b).
Similar to the reactions of AlEt3 and AliBu3 with partially
dehydroxylated silica, the reaction of [Et 2 AlCl] 2 with
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Figure 6. (a) IR spectra of -Al2O3 treated at dierent temperatures. (b) Assignment of the peaks observed in the IR. (c) OH density (in OH nm2)
and surface area (in m2 g1) as a function of temperature.
mobility increases, leading to a faster phase transition to /alumina. The presence of H2O (steam) above 700 C facilitates
the phase transition.355
Mesostructured -alumina can be prepared by solgel
process in the presence of structure directing agents and has
surface area ranging from 600800 m2 g1 and 2 nm pore
size.356358 Alumina obtained by ame pyrolysis of AlCl3, H2,
and O2, such as Aeroxide Alu C from Evonik, is a mixture of
and phases that have a lower surface area of around 120 m2
g1. Alu C is more stable and more IR transparent than pure alumina, which can be helpful to monitor the evolution of
surface sites, in particular because - and -alumina share
similar bulk and surface properties.
The presence of two types of Al-sites in the bulk reects on
the rich surface chemistry of -alumina surfaces. Surface
aluminum sites can be hexa- (AlVI), penta- (AlV), tetra(AlIV), and tricoordinate (AlIII). The surface also contains
terminal AlOH group bound to AlIV, AlV, and AlIV as well as
2- or 3-OH bridging between Al sites. The OH vibration
bands and the corresponding sites are summarized in Figure
6a,b, and beneath each structure is the OH of each AlOH.
These diverse surface functionalities give rise to a complex IR
spectrum of -alumina in the OH region (Figure 6a) and result
in a dierence of reactivity between each type of OH and Al
site. Similar to silica, applying a thermal treatment to alumina
under vacuum or inert gases leads to a decrease in the OH
intensity, indicating that the AlOH density decreases (Figure
6c). For example, Al2O3500 and Al2O3700 have an OH density
of 2.0 and 0.7 OH nm2, and fully dehydroxylated alumina can
be obtained at ca. 1000 C (Figure 6c). However, at 700800
C -alumina transitions to and phases according to powder
XRD diraction. This transition is also accompanied by a slight
loss of surface area (Figure 6c).
In contrast to silica, the overall shapes of the OH bands in IR
are not dramatically aected as a function of temperature,
indicating that the dierent AlOH sites in Figure 6b are
present at all treatment temperatures. The dehydroxylation

process is also accompanied by the formation of Lewis acidic
Al(III) sites that were shown to correspond to highly reactive
defect sites. These Al(III) sites appear in -alumina treated
above 400 C.354,359,360
The surface acidity of alumina is determined by the
adsorption of probe molecules and studying their spectroscopic
signatures by IR. The Lewis acidity depends on the number of
oxygen atoms bonded to the Al site. AlVI, AlV, AlIV, and AlIII will
all behave dierently from one another depending on the probe
molecule added. The most acidic sites in the alumina surfaces
have been assigned to AlIII sites based on the adsorption of
probe molecules such as pyridine, CO, H2 or CH4, and
N2.354,359,361364
Depending on the method of synthesis, -Al2O3 contains
dierent dominant facets. Understanding the population of
these facets is important to build periodic models that can lead
to deeper understandings of the -alumina surface. Transmission electron microscopy (TEM) studies of precipitated
(pseudo)boehmites usually show that lamellar and rhombic
crystal shapes are dominant. The (110) and (100) facets are
predominant for the lamellar particles, whereas the (110) and
(111) facets are predominant for rhombic particles.346 Alumina
from amed pyrolysis also expose mainly the (110) facet
(80%), but small amounts of the (100) and (111) facets are
also present.
For a more complete account of theoretical models of
alumina surfaces a recent review on the topic appeared.346
Spinel type models contain 37.5% tetrahedral Al-sites and 62%
octahedral Al-sites,365 values that are slightly dierent from
experimental measurements made on -alumina. An alternative
and now widely accepted model for the -alumina surface is
based on the dehydration of boehmite. This bulk model of Al2O3 consists of aluminum atoms in tetrahedral (25%) and
octahedral (75%) coordination sites with nonspinel sites
occupied. The unit cell of (110) termination at complete
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dehydroxylation (s0 surface) exposes one tricoordinate AlIII and

two types of tetracoordinate AlIV sites, namely AlIVa and AlIVb
(Figure 7). The AlIII site is trigonal planar, and the AlIVb sites
are tetra-coordinated with a truncated octahedral geometry
(Figure 7b). The experimentally less abundant (100)
termination exposes only AlV sites that adopts a pentacoordinated square-base pyramidal geometry (AlVa AlVd Figure 7a).
The s0 fully dehydrated surface (Figure 7b) is not a realistic
model because the -Al2O3 surface contains AlOH groups at
experimental pretreatment temperatures. In addition, thermodynamic calculations indicate that the surface energy of the fully
dehydrated (110) termination is higher (less stable) than that
of the (100) surface. This result indicates that the (110) facet of
the s0 surface is metastable, and strongly stabilized by
hydroxylation. These calculations also predict that s0 surface
should exist only above ca. 900 C,363 temperatures at which Al2O3 phase is not stable.354 The low stability of the dehydrated
surface combined with the higher mobility of O atoms at high
temperatures explains the change of phase upon high
temperature treatment.
Surface Sites and Probe Molecules. CO and pyridine are

typical probe molecules, which provide information about the
type and the strength of Lewis and Bronsted acid sites.346,361
Investigation of the adsorption of CO and pyridine on -Al2O3
by DFT calculations shows that AlIII and AlIV on the (110)
surface and AlV sites on the (100) surface are Lewis acidic and
follow the trend in strength of AlIII > AlIV > AlV.363,364 The
strong Lewis acidity of AlIII sites present on the (110) surface of
-Al2O3 is evidenced by its ability to coordinate N2. Combined
with the Lewis basicity of surface oxygen atoms, this site readily
promotes the heterolytic activation of CH4 and H2 (Figure 8).
In these cases, the degree of hydroxylation of the surface plays a
critical role in the reactivity of AlIII sites.354
Figure 8. Coordination of N2 and activation of CH4 and H2 occurring

on the AlIII defect sites of the (110) surface of -Al2O3.
3.2.2.2. Grafting Molecular Precursors on Alumina and

Resulting Surface Species. Generalities. Ballard25,118 and
Burwell26 recognized that alumina supports often led to more
active and stable single-site catalysts. Grafting on alumina can
take place on surface AlOH groups, or directly on Lewis
acidic Al-sites. Often grafting involves more than one site on
the alumina surface, which leads to a mixture of organometallic
sites, making structural determination more complex than on
silica. In addition, molecular analogues of alumina surface sites
are not readily available. We describe a comprehensive list of
grafted compounds and give a more detailed analysis on
selected examples.
Alumina-Supported Early Transition Metal (Group 46)
Complexes. Grafting homoleptic MRn complexes on partially
dehydroxylated alumina has been investigated since the early
seventies.25 Seminal studies on alumina-supported lanthanide
and actinide complexes were reported in the eighties.14
Zr(CH2tBu)4 is a representative example that shows the
dierence between organometallic sites supported on silica and
alumina. The reaction of Zr(CH2tBu)4 with Al2O3500 results in
the mixture of surface species shown in Scheme 19a.370
Protonolysis of the alkyl ligand also occurs to form (AlSO)Zr(CH2tBu)3 and (AlSO)2Zr(CH2tBu)2, analogous to the
reactivity of Zr(CH2tBu)4 with partially dehydroxylated silica.
However, these surface species further react with adjacent
Lewis acidic Al-sites by abstracting an alkyl group to yield
cationic Zr surface species along with alkyl aluminate,
[(AlSO)2ZrCH2tBu+][AlSCH2tBu] (Table 3, entry 1). This
reactivity behavior was observed in many Zr370 and Hf371,372 d0
complexes, including mono- or bis-cyclopentadienyl complexes222 (Scheme 19b,c and Table 3, entries 16).
The product distribution obtained from the reaction of Taorganometallic complexes and partially dehydroxylated alumina
depends strongly on the molecular precursor and the thermal
Figure 7. (a) (100) surface of -Al2O3 (2 1 unit cell) showing the

dierent AlV sites, (b) (110) dehydrated surface of -Al2O3 (s0
surface), and (c) (110) hydrated surface of -Al2O3 (3.0 OH nm2)
with water adsorbed on AlIVa, on which the AlIII and AlIVb sites are
available.
Dierent degrees of hydroxylation have been modeled for

the (110) facet of the alumina surface with OH densities of 3.0,
6.0, and 9.0 OH nm2. At low coverage (3.0 OH nm2) the
most stable surface has water adsorbed on AlIII sites. However,
if the water molecule is split across two AlIVa sites, a relatively
stable surface containing a free AlIII site is accessible (Figure
7c). This surface exposes the highly reactive AlIII defect site that
binds N2 and readily reacts with H2 or CH4. Such Lewis acid
sites are also able to convert CH3F and CH3OCH3 to olens
(e.g., isobutene) via carboncarbon bond formation step
involving adjacent Lewis acid sites.366,367
In contrast, the intrinsically more stable (100) termination is
free of water at much lower temperatures (ca. 350 C; Figure
7a). The (111) surface can be exposed, too, but its relevance
depends on the synthesis conditions.368 Nanoscale facets of this
surface have been proposed to form upon reconstruction of the
(110) surfaces.369
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Scheme 19. Grafting Zirconium and Hafnium Complexes

onto Al2O3
Scheme 22. Grafting by CH bond activation
and Table 3. This is a result of direct transfer of the methyl

group to Lewis acidic Al sites, which can presumably take place
in the absence of AlSOH groups in highly dehydroxylated
alumina (Table 3, entries 910).226
The less electrophilic W(CtBu)(CH2tBu)3 reacts with
Al2O3500 selectively on the most reactive AlIVOH sites to form
[(OS)3AlIVO]W(CtBu)(CH2tBu)2 with the alkyl and alkylidyne fragments interacting with nearby AlSOH groups
according to IR and NMR spectroscopies (Scheme 21a,
Table 3, entry 11).370,374 With [W(OEt)5]2, grafting on
Al2O3500 generates the corresponding grafted dinuclear
W(V) complex (Scheme 21b, Table 3, entry 12).190 Other W
complexes have been adsorbed on Al2O3, but the nal structure
has not been studied in detail.375
Grafting MeReO3 on Alumina. MeReO3 is stable in acidic
aqueous media and has a relatively acidic methyl group with a
pKa of ca. 10.376 In contrast to most organometallic complexes,
MeReO3 reacts with partially dehydroxylated alumina to form
oxo-bound (8590%) as well as -methylene surface species
(1015%) as shown in Scheme 22a. These assignments are
based on extensive solid-state NMR, XAS, and computational
studies.377,378 Grafting through the heterolytic activation of a
CH bond in MeReO3 is similar to what is observed for the
reaction of H2 and CH4 on defect Al sites.354,359 Calculations
indicate that the CH bond activation involves two adjacent Al
sites that generate the -methylene species. A similar grafting
involving CH bond activation was also proposed for
CpMo(CO)3CH3 (Scheme 22b).379
Alumina-Supported Late Transition Metal Complexes. As
found for silica, late transition metal complexes react with
alumina by displacement of an anionic ligand as shown in Table
3. No evidence of the formation of cationic species has been
reported so far. Grafting mononuclear and dinuclear Fe(II) aryl
molecular complexes on Al2O3500 generates the corresponding
mono- and dinuclear monografted surface species for Fe (Table
3, entries 1314).128 Although the corresponding gold complex
[Au(Mes)]5 grafts on alumina, grafting is accompanied by
spontaneous formation of nanoparticles, presumably because of
the hydrolysis of the complex into AuOx, which then transforms
into Au nanoparticles.129 Ni(allyl)2,125 Rh(allyl)3,126 and
Ir(allyl)3380 also generate the corresponding monografted
metal complexes on Al2O3 (Table 3, entries 1517). While
complexes containing the OSi(OtBu)3 ligand, as in [(COD)Ir(OSi(OtBu)3)]2, also graft on alumina, the HOSi(OtBu)3
formed upon grafting remains adsorbed at the surface, possibly
due to a strong interaction of the silanol and Lewis acidic Alsites (Table 3, entries 1819).381
3.2.3. SilicaAlumina Supported Metal Complexes.
3.2.3.1. General Considerations on SilicaAlumina. Silica
aluminas or aluminosilicates are much more complex materials
because they exhibit the combined properties of silica and
alumina. This class of materials also includes zeolites; welldened complexes supported on zeolites have been comprehensively reviewed recently and will not be discussed here.19
Silicaalumina can be prepared by coprecipitation,383 sol
Scheme 20. Grafting Tantalum Complexes onto Al2O3
Scheme 21. Grafting Tungsten Complexes onto Al2O3
pretreatment of alumina. Ta(CHtBu)(CH2tBu)3 reacts with

the surface hydroxyls of Al2O3500 to form mainly (AlSO)Ta(
CHtBu)(CH2tBu)2 as shown in Scheme 20a (Table 3, entry
8).373 However, the reaction of Cp*Ta(CH3)4 and Cp2Ta(CH3)3 with Al2O31000 yields [Cp*TaMe3+][AlSMe] and
[Cp2TaMe2+][AlSMe] ion-pairs as shown in Scheme 20b,c
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Table 3. Well-Dened Alumina-Supported Surface Complexes
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Table 3. continued
Degussa Aeroxide AluC (100 m2 g1). bJohnson Matthey -Boehmite monohydrate (200 m2 g1). cAmerican Cyanamid, PHF (150 m2 g1).
SASOL SBa
gel,384386 or thermolysis of molecular precursors.387389 These

materials contain Al and Si both in the bulk and on the surface.
Silicaalumina surfaces can also be prepared by surface doping
of the corresponding pure oxides with Al- or Si-precursors by
ion deposition/exchange390 or grafting Al(OR)3 or Si(OR)4
followed by a thermal treatment.72,387389 In general the surface
is dominated by the presence of silanols that have similar IR
signatures to those observed in silica, albeit with slightly
broader bands. The broadening can be attributed to silanols
interacting with, or in close proximity to, Al sites.384,391393 The
other possibility is that silanols are interacting with adjacent
distorted Si Lewis acid sites.394 The surface also contains Lewis
acidic Al-sites according to acetonitrile, pyridine, and CO
adsorption studies.51,391393,395 In some cases OH groups

bonded to Al centers are observed by IR spectroscopy.393,396
Their presence and relative amount highly depends on the
mode of preparation of silicaalumina.383,391
A periodic model of silicaalumina was constructed by
placing an epitaxial silica lm on the dehydrated (100) surface
of -Al2O3, which corresponds to a coverage of Si (Si) of 6.4
nm2.394,397 Annealing this model to 1023 K using force eld
molecular dynamics forms a mixed amorphous silicaalumina
(ASA) surface. During the annealing some Al atoms are
extracted from the -Al2O3. The extracted Al atoms are either
AlV (II1, III3) or AlIV (III1, III2, III4) shown in Figure 9a. These
results were in agreement with 27Al MAS NMR data.391,398400
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Here we show idealized average structures based on available

spectroscopic assignments.
Using a combination of IR, computational and solid state
NMR techniques, it was proposed that chemisorption of
CH3ReO3 on silicaalumina at low rhenium loading aords a
rhenium surface species grafted via Lewis acid/base interactions
between rhenium and a surface oxide moiety and a rheniumoxo group and a surface Al (Scheme 23a).403 At higher rhenium
loading, a second distinct species is formed, consisting of
hydrogen bonded CH3ReO3 on the surface hydroxyl groups,
this second species being inactive in alkene metathesis (Scheme
23b).404
Scheme 23. Proposed Surface Sites for CH3ReO3 on Silica
Alumina Systemsa
Sites (a) are solely observed at low rhenium loading; both (a) and
(b) present at higher loading.
3.2.4. Other Supports. Other pure oxides, in particular

MgO, TiO2, and CeO2, have been used to graft molecular
precursors, though to a lesser extent.
3.2.4.1. Magnesia MgO. The surface chemistry of MgO
has been studied in some details. MgO is an ionic solid with
terraces and irregularities on the (100) termination that impact
its reactivity.411 The MgO surfaces have been modeled by DFT
periodic calculations.412,413 Adsorption of water on edges is
much stronger than on terraces, and two kinds of hydroxyls
were assigned, appearing at 3749 and 37373690 cm1,
corresponding to terminal MgOH (Type A) or bridging
multicoordinated Mg-(OH)-Mg (Type B) groups as shown in
Figure 10a.414 The assignment is represented in Figure 10b.
Subsequent computational analysis on a large variety of surface
sites proposed a dierent assignment.413 The study showed that
the most important parameter for determining the stretching
frequency of a given OH group is hydrogen bonding: the
signals showing the highest frequencies corresponded to
terminal isolated OH groups of type C (present in kinks and
step divacancies) and hydrogen-bond acceptor OH groups.413
The second parameter to take into account is the location of
OH groups in concave or convex areas of the surface of MgO,
resulting in various interactions of the hydroxyl with its
environment. In contrast to previous studies, the coordination
of the oxygen of the hydroxyl appears to be a less important
parameter. Overall, the high-frequency side of the sharp band in
the IR of MgO involves monocoordinated hydrogen-bond
acceptors hydroxyls (type C), whereas its low frequency side
involves multicoordinated isolated OH groups (type B) and
dicoordinated hydroxyls of types A and C, labeled as A and C
in Figure 10b. The broad band between 32003650 cm1 is
assigned to hydrogen-bond donor OH groups (type D).
MeMn(CO)5 was reported to react with MgO400 with
release of methane (Table 5, entry 1). According to EXAFS, the
MgO surface behaves as a bidentate ligand providing
coordination of an additional oxygen atom. The latter is
further evidenced by a loss of one CO ligand. Late transition
metals could be also grafted onto MgO surface, although the
Figure 9. (a) Top view of the amorphous silicaalumina with an OH

coverage equal to 5.4 OH nm2 showing the pseudobridging silanols
interacting either with Si or Al centers (PBS-Si and PBS-Al,
respectively). (b) Side view of the amorphous silicaalumina surface.
When water molecules were added to the system the formation

of silanols was energetically preferred over the formation of Al
OH groups, silanols being the only surface hydroxyl up to 4.3
OH nm2. Increasing the OH coverage to 5.4 OH nm2 is
more representative of the real surface structure (Figure 9a).
The surface contains silanols interacting either with Si or with
Al centers. These pseudo-bridging silanols (PBS-Si and PBSAl if the interaction of the silanol is with a Si or Al center,
respectively) could be responsible for the milder acidity of ASA
compared to zeolites. The model presents one kind of PBS-Si
between the U1 and V2 centers and three dierent of PBS-Al
between the Z2-III2, Y2III4 and V1III3 centers; it was recently
validated by DNP SENS.72 This surface was used in order to
evaluate the Brnsted acidity of silicaalumina by means of
DFT calculations using CO, pyridine, lutidine and ammonia as
probe molecules.401,402
3.2.3.2. Grafting Molecular Precursors on SilicaAlumina.
Generalities. Though the surface chemistry of silicaalumina is
not fully understood, several organometallic complexes were
supported on amorphous silicaalumina to form well-dened
sites. The surface chemistry resembles that of silica; grafting
occurs primarily on surface silanols. With silicaalumina
partially dehydroxylated at 500 C, the major species are
typically monografted. The surface species have similar
spectroscopic signatures as the corresponding silica-supported
species. However, silicaalumina supported species can display
signicantly dierent reactivity than silica-supported organometallics, often closer to alumina supported species (see
sections 3.4 and 4). These surface species are shown in Table 4.
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Table 4. Silica-Alumina-Supported Perhydrocarbyl Surface Species
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Table 4. continued
a
Akzo-Nobel (HA-S-HPV, Si/Al 75/25, 480 m2 g1). bKetjen (Si/Al 75/25, 375 m2 g1). cEstimated value. dStructure proposed based on analogy to
other surface species.
While most immobilized metal complexes on TiO2 were

prepared by grafting through phosphonate-derived ligands,424427 there are only few examples of a direct bond
between the metal sites and the surface. Contradictory results
were obtained on grafting Rh(allyl)3 (Rh-1) onto titania surface
(Scheme 24). While bis-grafted species Rh-1Tb have been
claimed on TiO2200 on the basis of TPD of the grafted
complex (Table 5, entry 7),420 quantication of propene
evolved during grafting of Rh-1 on TiO2250 is consistent with
the formation of monografted species Rh-1Tm, analogously to
what is observed on silica (Table 5, entry 6).126 Au(acac)Me2
was reported to react with TiO2400.421 Although the detailed
structure of the resulting surface complex was not elucidated,
XAS study indicated presence of site-isolated mononuclear AuIII
species on the surface. Surface species obtained via grafting
V(NMe2)4 onto TiO2180 were studied by EPR and elemental
analysis, which supports the formation of tris-grafted complex
(TiSO)3V(NMe2).163
3.2.4.3. Ceria CeO2. CeO2 is a support with the ability of
storage and release of oxygen due to its defective nature.428
Grafting Au(acac)Me2 onto CeO2400 was studied by XANES/
EXAFS, which conrmed the formation of monografted
complex (CeSO)(OS)AuMe2 with additional OS-atom coordinated to gold.422
3.2.4.4. Indium Tin Oxide (ITO) In2O3:Sn. Reaction of Ir10 with conductive ITO is proposed to generate Ir-10ITO, a
surface species able to catalyze the electrochemical water
oxidation in acidic solutions with activities higher than the bulk
IrOx (Scheme 25).429 The molecular identity of the surface
layer was demonstrated indicating that choice of ligand could
allow control over the activity.
3.2.4.5. Magnesium Chloride MgCl2. The industrial
ZieglerNatta catalyst contains TiCl4 supported on MgCl2 that
is activated with AlR3 reagents. To study well-dened models
for this catalyst several groups have synthesized high surface
area MgCl2 solvates of alcohols430432 and ethers433,434 and
contacted this material with TiCl4. Contacting MgCl2THF1.5
with TiCl4 forms the TiCl4/MgCl2/THF precatalyst. Solid-state
NMR analysis of TiCl4/MgCl2/THF showed that THF
coordinated to Ti(IV) centers ring-opens to form the surface
species shown in Scheme 26.435 Activation of this material by
AlR3 reagents reduces the Ti(IV) center to Ti(III) according to
XAS436 and EPR437 studies, but the structure of active sites
remains to be understood.
Figure 10. (a) Proposed OH groups on MgO (A, B, C, and D types).

(b) Assignment of the OH frequencies on MgO.413,414 A and C
correspond to A and C types of OH groups in which Mg is bonded to
dicoordinated oxygen atoms.
reactivity of partially dehydroxylated magnesia toward Rh(allyl)3, studied by IR spectroscopy and quantication of gases
evolved, was found to be much lower compared to silica,
alumina, and titania.126 This is in line with lower pKa values of
surface MgOH groups. Thus, similarly to what is observed for
silica, late metal alkyls display low reactivity toward surface
hydroxyls and complexes bearing anionic O-ligands are
preferred for grafting. More recently a series of well-dened
magnesia-supported Rh, Ir, and Au complexes was reported
(Table 5). Grafting of metal acetylacetonates leads to
elimination of acac ligand and formation of isolated
monografted surface species. In all cases interaction with an
additional surface oxygen atom was evidenced by EXAFS.
Although released Hacac reacts with magnesia and remains at
the surface, and thus cannot be quantied, changes in IR
vibrations and bond distances given by EXAFS conrm
grafting. In contrast to single-site late transition metals on
other supports, Rh and Ir magnesia-supported species stay welldispersed under H2 and CO, leading to bis-carbonyl species in
the latter conditions.
3.2.4.2. Titania TiO2. TiO2-anatase crystals are dominated
by (101) surfaces as a major facet, the (001) being a minor
one.423 The highest frequency in the IR of TiO2-anatase was
assigned to TiV-1OH groups located on the (001) surface,
whereas the lowest one was assigned to TiVIOH2 located on
the (101) surface.
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Table 5. Well-Dened Surface Complexes on MgO, TiO2, and CeO2
Nominal value.
Scheme 24. Grafting Rh(allyl)3 onto TiO2
Scheme 26. Ring Opening of THF in TiCl4/MgCl2/THF
3.2.4.6. Sulfated Metal Oxides. Sulfated alumina and

zirconia are prepared by exposing the parent oxide to aqueous
solutions of sulfuric acid followed by calcination in air.438,439
Sulfated zirconia was reported to isomerize alkanes at lower
temperatures than sulfuric acid.438,439 Several studies showed
that the acidic sites on sulfated zirconia are less acidic than the
bridging hydroxyls in zeolites.440 The catalytic reactivity of
sulfated zirconia itself is probably not related to the acidity of
these sites but rather to the redox activity and/or the
noncoordinating nature of surface sulfate species of this
support.441 Computational studies are consistent with the
experimental data, showing that the reaction of the (101) and
(001) surfaces of tetragonal ZrO2 with H2SO4 results in the
protonatation of the oxide with H2SO4 to form the acidic sites
shown in Figure 11.442 The most stable congurations contain
Scheme 25. Electrochemical Water Oxidation with a

Heterogenized Ir Catalyst
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Scheme 27. (a) Organometallic Complexes and (b) Their

Reaction with Sulfated Alumina
observations were made for organozirconium species supported

on sulfated zirconia447 and sulfated tin oxide.448 In general,
complexes supported on sulfated metal oxides have high
quantities (>60%) of active sites according to quantitative
poisoning studies, and in some cases 100% active site
concentration was determined.446,449
DFT calculations were performed on a model of the sulfated
alumina surface using the previously described (110) surface of
-Al2O3.446 The sulfated alumina model was constructed by
determining the lowest energy structures for the adsorption of
H2SO4 on the (110) surface of alumina as an exchange/
condensation reaction with the OH groups on the -Al2O3
surface. The most stable structure was dehydrated at 550 C as
in the experimental synthesis of sulfated alumina. The model
contains 3.0 H2SO4 per nm2 and a hydroxyl coverage of 4.4 OH
per nm2. The surface presents two type of sulfate ions (SA and
SB) adsorbed on the alumina surface, as shown in Figure 12.
Grafting of Cp*ZrMe3 on sulfated alumina was evaluated by
DFT calculations using the model in Figure 13. The most
stable geometry for the ZrMe protonolysis was favored on the
acidic OH group coordinated to three Al atoms ((Al)3OH
species). The organozirconium surface species was modeled by
placing the cationic Cp*ZrMe2+ on the deprotonated sulfated
alumina surface on either the SA or the SB surface sites. The
interaction with SA forms a structure with a ZrO distance of
2.24 . Grafting on the SB site results in the interaction of
Cp*ZrMe2+ on two SO groups with a mean ZrO distance
equal to 2.36 . These calculations result in a geometry that is
in good agreement with the EXAFS and NMR data. Benzene
interacts with Cp*ZrMe2+ on either SA or SB sites to form
Cp*ZrMe2(C6H6)+, in which the benzene inserts into the Zr
O bond with a ZrC(benzene) mean distance equal to 2.71 .
This value is larger than the value obtained by EXAFS (2.35 ).
In this structure the Zr center is displaced away from the SA and
SB surface sites.
Figure 11. Most stable congurations of the H2SO4 adsorption on the

ZrO2 (101) and ZrO2 (001) surfaces. (a) Top and perspective views of
the optimized structure of the 2H+ and SO42 species adsorbed on the
ZrO2 (101) surface. (b) Top and perspective views of the optimized
structure of H+, OH, and SO3 species adsorbed on the ZrO2 (001)
surface.
a sulfate anion (SO42) that coordinates to three surface

zirconium atoms and two protons adsorbed onto two surface
oxygen atoms on the (101) facet (Figure 11a). The most
favorable adsorption product on the ZrO2 (001) contain similar
features, a 3-fold coordinate SO42 anion and two protons
bound to surface oxygen atoms (Figure 11b). This study was
extended by evaluating the adsorption of H2O and SO3 (or
H2SO4) on the (101) surface of ZrO2 for higher coverages.443
Similar models have been developed for sulfated alumina (AlS,
Figure 12).446
3.3. Evolution of Well-Dened Surface Sites upon

Post-Treatment and/or Functionalization
Figure 12. Sulfated -Al2O3 model (AlS) based on DFT calculations

presents two kinds of surface sites (SA and SB).446
3.3.1. Calcination. Calcination is a treatment at high

temperatures (above 400 C), typically performed under air.
This step is common in the preparation and/or the
regeneration of heterogeneous catalysts because this removes
carbon-containing species, including organic ligands. Oxidation
catalysts including single-site supported systems are often
stabilized by a calcination step; prototypical examples are the
calcination of grafted cyclopentadienyl21 and other162 Ti
derivatives as a method to generate isolated Ti(IV) surface
sites. By and large, surface sites remain isolated upon
calcination, particularly for early and rst row transition metals
and when low surface loadings are used. This approach is
general to OSi(OtBu)3 complexes and provides isolated
The reaction of Cp*MR3 or M(CH2Ph)4 (M = Ti, Zr, Hf; R

= Me, Ph, CH2Ph) with sulfated alumina forms weakly
coordinated ion pairs with the surface as shown in Scheme
27.444446 For example, the reaction of Cp*ZrMe3 with sulfated
alumina forms the surface bound Cp*ZrMe2+ ion according to
13
C CPMAS NMR spectroscopy, which contains characteristic
resonances associated with cationic ZrMe+ complexes. In
addition, X-ray absorption spectroscopy established that a long
ZrO contact was present in Cp*ZrMe3/AlS indicating that
the surface acts as a weakly coordinating anion. Similar
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Figure 13. Cp*ZrMe2+ complex on the (a) SA-SB and (b) SB sites. (c) Insertion of benzene into the ZrO bonds of the grafted Cp*ZrMe2+ species
and displacement from the SA and SB sites.
3.3.2. Thermolysis under Vacuum or Inert Gas.

Supported species containing N(SiMe3)2, OSi(OtBu)3,
OtBu, or Cl ligands can readily lose their ligands when
treated at high temperatures (>150400 C) under vacuum,
while remaining isolated sites. This thermolysis step involves
the reaction of the metal sites with adjacent siloxane bridges
and generates more stable silicate species. For instance, silicasupported metal chloride evolve upon heating under vacuum to
form bis- and tris-grafted species as shown in Scheme
29a.203,274 The silica-supported dimeric Cr(II) Cr-6m forms
the corresponding dinuclear Cr(II) Cr-6T complexes at 300
400 C under vacuum (Scheme 29b).198 XANES of the
Ti(IV), Ta(V), and Fe(III) sites as shown in Scheme

28.193,199,450 Calcination at high temperatures can also lead to
incorporation of the metal into the support matrix and/or to
sintering to form metal oxide clusters.193,451
Scheme 28. Calcination of Grafted Surface Species
Scheme 29. Evolution of Surface Species upon Thermolysis under Oxygen-Free Conditions
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Scheme 30. (a) Hydrogenolysis of Supported Alkyl Complexes and (b) Surface Hydrides of Group 46 Metals on Various
Supports
Table 6. Early Transition-Metal Hydrides (Group 46) and Their Characteristic IR Signatures
compound
name
MH (cm1)
refs
(SiO)3TiH
(Si/AlO)3TiH
(SiO)3ZrH
(SiO)2ZrH2
(Si/AlO)3ZrH
(AlO)3ZrH
(SiO)3HfH
(SiO)2HfH2
(SiO)Hf(Np)H2
(Si/AlO)3HfH
(AlO)3HfH
(SiO)2TaH
(SiO)2TaH(PMe3)
(AlO)2TaH
(ZrO)(SiO)TaH
(SiO)2WHn (n = 24)
(Si/AlO)2WHn (n = 24)
(AlO)2WHn (n = 24)
TiSiO2-H-1
TiASA-H-1
ZrSiO2-H-1
ZrSiO2-H-2
ZrASA-H-1
ZrAl2O3-H-1
HfSiO2-H-1
HfSiO2-H-2
HfSiO2-H-2-R-1
HfASA-H-1
HfAl2O3-H-1
TaSiO2-H-1
TaSiO2-H-1-P
TaAl2O3-H-1
TaZrO2/SiO2-H-1
WSiO2-H-n
WASA-H-n
WAl2O3-H-n
1706,1692,1679,1647
16001725
1633
1649, 1622
1635(br)
1622
1701
1720, 1675
1685, 1651
1702, 1675(sh)
1670
1830,1815(sh), 1855(sh)
1687
1830
1800
1960, 1815
1948,1819
1903, 1804
132
405
136,455457
457,458
406
459
460,461
461
461
142
462
299,463
454
373
464
465
409
373
3.3.3. Thermal Treatment under H2. The reaction of

silica, alumina, and silicaalumina supported early transitionmetal homoleptic alkyl complexes discussed in sections 3.2.1.2
with H2 at 100200 C typically forms metal hydrides shown
in Scheme 30a. The MH vibrations are summarized in Table 6.
At higher reaction temperatures under H2, the MH band in the
IR spectrum decays while the SiH bands increase in intensity,
indicating that hydrides are transferred to the surface and that
the metal incorporates into the oxide support.452,453 For
instance, (SiO)2TaH forms (SiO)3Ta and additional
surface SiH. (SiO)3Ta coordinates PMe3 and stoichiometrically reacts with O2.454
molecular Cr(II) dimer Cr-6 and Cr-6T are remarkably similar,

indicating that Cr-6T remains Cr(II) and is dimeric after
thermal treatment. This approach also applies to monomeric
Cr(III) containing Cr-5, which forms the monomeric Cr(III)
silicate Cr-5T shown in Scheme 29c.197 Contacting Cr-5T with
CO results in two CO bands in a 60:40 ratio, indicating that
two species are present on the surface. These two species
correspond to tricoordinate Cr(III) sites (60%) and tetracoordinate Cr(III) sites that interact with a nearby siloxane
bridge. A similar thermolysis step under vacuum at 500 C
converts (SiO)Ln(N(SiMe3)2 into (SiO)3Ln as shown in
Scheme 29d.88
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trimethylsilylamide complexes, also form particles in the

presence of H2 and also passivate the regenerated OH groups
of the support to yield supported nanoparticles on silica having
no OH groups.159,168,216
There are a few examples of stable late metal hydrides
supported on oxides. Rh249 and Ir23,250 surface complexes
containing phosphine ligands generate the corresponding
surface hydrides (Scheme 32b). In addition, some Ir metal
complexes supported on TiO2 and CeO2 lead to isolated metal
ions upon treatment under H2.417 [M(COD)(COT)] (M= Ru
and Os) graft onto surface SiH functionalities and react with
H2 to generate discrete well-dened metal hydrides (Scheme
32c).469
3.3.4. Thermal Treatment under H2S. The reaction of
H2S on well-dened W surface sites was explored in the eighties
to prepare supported Ni-promotod W sulde hydrodesulfurization (HDS) catalysts.470,471 [W(OEt)5]2 supported on silica
alumina undergoes suldation in the presence of H2S below
150 C, a temperature much lower than needed to promote the
suldation of supported polyoxometallates, forming hexagonal
WS2 plates as shown in Figure 14. The formation of this phase
is attributed to the milder suldation conditions, is probably
kinetically controlled and yields the catalyst much more active
in the hydrogenation of toluene.190
The formation of supported metal hydrides probably occurs

through hydrogenolysis of MC bonds to form highly reactive
MH species, which further react with the adjacent siloxane
bridges in the case of silica or alternative 2-O functionalities
present in alumina and silicaalumina. This process creates
new MO bonds and transfers hydrides to the surface. For
example, (SiO)Zr(CH2tBu)3 reacts with H2 to form (
SiO)3ZrH and (SiO)2ZrH2 in a 60:40 ratio with the
concomitant formation of SiH and SiH2 species as shown in
Scheme 30.457 Similar results were obtained for Ti405 and
Hf.462 Though in the specic case of Ti, Ti(III) surface species
are also formed.405 (SiO)Ta(CHtBu)(CH2tBu)2 reacts
with H2 at 150 C to form (SiO) 2 TaH and (
SiO)2TaH3.299 Further heating these species above 200 C
leads to loss of the hydride ligands and formation of (
SiO)3Ta (TaSiO2) (Scheme 31).
Scheme 31. Thermal Treatment of TaSiO2-H-1
3.4. Stoichiometric Reactivity and Activation of Small

Molecules on Well-Dened Surface Sites
Not all supported species form stable hydrides. The reaction

of (SiO)W(CtBu)(CH2tBu)2 with H2 leads to recovery of
surface silanols and formation of presumably W-containing
surface aggregates.409 However, the reaction of (AlSO)W(
CtBu)(CH2tBu)2 with H2 forms stable (AlSO)W(O)(H)3
species.466 Alumina-supported alkyl aluminum species also lead
to the formation of aluminum hydride surface species upon
reaction with H2 at 200 C.467 Hydrides of Ti,405 Zr,406 Hf,142
Ta,373 and W hydrides409 are also formed on silicaalumina as
evidenced by IR spectroscopy (Table 6), but their structures
remain undetermined.
Most late transition-metal species supported on SiO2, Al2O3,
MgO, or TiO2 react with H2 to yield small metal nanoparticles
(Scheme 32a).213,218,247,381,468 Supported late or coinage metal
3.4.1. Stoichiometric Ligand Exchange via Protonolysis Reactions with Brnsted Acids. Treatment of surface
alkyls, amides, hydrides, and other complexes with Brnsted
acids leads to substitution of the ligands via protonolysis and
gives the corresponding ligand exchanged products. This
methodology is widely applied to generate surface alkoxides
(Scheme 33), carboxylates, and acetylacetonates from welldened surface species.131,137,155,179,183,186,253,271,472474
3.4.2. Reactions with Lewis Bases. Small molecules such
as CO, CO2, and N2 are probes for post-treated surface sites.346
These probes have specic IR and NMR signatures that provide
detailed information about the structure of the surface site. In
addition, these signatures can be compared with literature
precedents, and now be reliably calculated using computational
methods.83,84,384 For instance, CO stretching, pyridine CC
vibration361,384,475 and 15N chemical shifts476478 provide direct
information about the nature (Lewis, Brnsted vs H-bonding)
and the strength of the acid sites. R3P or the oxide derivatives
can also be similarly used as probe molecules.479
3.4.3. Coordination and Activation of N2. N2 is a very
weak -donor ligand that binds to strong Lewis acid sites or
metals that have strong back-bonding properties.480,481 N2
binds to Al(III) defect sites on the surface of Al2O3 and has
a very distinctive IR signatures.360 N2 also binds (SiO)2TaH,
and reacts in the presence of H2 to split N2 to form (
SiO)2Ta(NH)(NH2) at a single metal center as shown in
Scheme 34.482,483 (SiO)2Ta(NH)(NH2) can be independently synthesized from reaction of (SiO)2TaH (TaSiO2H-1) with NH3.484 Computations suggest that coordination of
H2 decreases the energy of activation of N2 by avoiding changes
to the oxidation state of Ta.482
3.4.4. Activation of O2 and N2O. (SiO)3Ta (TaSiO2)
reacts with 0.5 equiv of O2 to yield the corresponding Ta(V)
oxo species, (SiO)3Ta(O) (TaSiO2-O) without the
detection of reaction intermediates (Scheme 35a).452 (
SiO)3ZrH (ZrSiO2-H-1) and (SiO)2ZrH2 (ZrSiO2-H-2), react
Scheme 32. (a) General Synthesis of Supported Metal

Particles from Isolated Metal Sites on Oxide Surfaces; (b)
Isolated Late Metal Complexes That Are Stable Under H2;
(c) Site Isolated Ru Hydride
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Figure 14. Formation of WS2 from well-dened grafted W sites: inuence of the preparation method on the morphology and the hydrogenation
activity.
Scheme 33. Stoichiometric Protonolysis of Surface

Complexes
Scheme 35. (a) Reaction of TaSiO2 with O2; (b) Reaction of

ZrSiO2-H-1/2 with N2O; and (c) Reaction of Cr-6T with N2O
Scheme 34. Nitrogen Activation by Silica-Supported Ta

Hydrides
cleanly with N2O to yield (SiO)3Zr(OH) (ZrSiO2OH-1)

and (SiO)2Zr(OH)2 (ZrSiO2OH-2) (Scheme 35b).457 For
(SiO)4Cr2 (Cr-6T), the reaction with N2O at room
temperature yields a dinuclear Cr(III) silicate (SiO)6Cr
(Cr-6T-Ox) shown in Scheme 35c.198 This reactivity was
conrmed by the reaction of the molecular [Cr(OSi(OtBu)3)2]2 with N2O, which forms an isolable Cr(III) siloxide
dimer. The XANES of the Cr(III) siloxide dimer and Cr-6TOx are similar, indicating the similarities between both
structures.
3.4.5. Activation of CO2. The reaction of CO2 with (
SiO)3ZrH (ZrSiO2-H-1) and (SiO)2ZrH2 (ZrSiO2-H-2) forms
(SiO) 3 Zr(O 2 CH) (Zr SiO2 -O 2 CH-1) and (SiO) 2 Zr(O2CH)2 (ZrSiO2-O2CH-2) (Scheme 36).457 This reaction
also yields some methoxy surface species, suggesting that either
a small amount of a tris-hydride (SiO)ZrH3 is present or
alternatively two Zr sites are close to each other on the surface.
3.4.6. Stoichiometric Reactions with Ketones. Ketones
can also be used to probe surface sites, in particular surface
alkylidene (Scheme 37a) and imido complexes (see section 4.3
for other examples). For example, di-t-butylketone reacts with
(SiO)Ta(CHtBu)(CH2tBu)2 (Ta-12m) to form 2-t-butyl3,3-dimethyl-1-butene quantitatively (Scheme 37a).289 Fluo-
renone reacts with (SiO)Sm(N(SiMe3)2) by single electron

transfer to form Sm-2m-Fluor (Scheme 37b).182
3.4.7. Stoichiometric Reactions with Alkanes. Alkanes
react with (SiO)3MH and (SiO)2MH2 (M = Ti, Zr, Hf) to
form (SiO)3MR and (SiO)2M(R)2.455,485,486 This
reaction takes place on d0 metal hydrides by -bond metathesis
(Scheme 38a).487 The reaction of (SiO)2TaH and methane
at 300 C forms methyl, methylidene, and methylidyne surface
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evolves upon heating to produce additional H2 and (

SiO)2TaCp complex (Scheme 38c).490
Scheme 36. Reaction of Silica-Supported Zirconium

Hydrides with CO2
4. CATALYTIC ACTIVITY AND APPLICATIONS

4.1. Hydrogenation of Alkenes, Alkynes, and Arenes
Oxide-supported metal hydrides (or alkyls as precursors to

hydrides) are ecient hydrogenation catalysts. Early examples
include organoactinide complexes supported on -alumina,14,491
and group 5 homoleptic complexes supported on silica.492
These catalysts hydrogenate arenes to their saturated analogues
at high H2 pressures. Catalysts containing organometallic Zrcomplexes on sulfated alumina were reported to hydrogenate
arenes at 1 atm H2 pressure at 25 C giving turnover
frequencies up to 360 h1.445,446,449 Titration studies showed
that nearly 100% of the sites were active.446 The reaction of
Cp*ZrMe3/AlS with H2 forms Cp*ZrH2/AlS that are the
active species in this reaction. The proposed mechanism is
shown in Scheme 39. Cp*ZrH2/AlS contains a weak ion pair
with the AlS surface that allows for benzene coordination.
Cp*ZrH2/AlS reacts with benzene to give the insertion
products, which further react with H2 by turnover limiting bond metathesis to give the cyclohexadiene complex.
Subsequent hydride transfer and ZrC hydrogenolysis steps
give cyclohexane.446 The hydrogenation of arenes is sluggish
with the isostructural Ti or Hf complexes, or tantalum
organometallics, grafted onto sulfated supports.
Late transition metals supported on oxides generally evolve
to metal nanoparticles and hydrogenate a broader range of
substrates (see section 3.3). However, late transition metal
hydrides can be stabilized by additional ligands, and these
species are active in the hydrogenation of olens as shown in
Scheme 40.23 For example, silica-supported Rh hydride Rh-9m
catalyzes the hydrogenation of cis-2-butene to butane (Scheme
40a).127 The semihydrogenation of alkynes was also reported
for supported Pd complexes (Scheme 40b), which presumably
occurs through formation of PdH species.247 Silica-supported
Ir hydride Ir-6m stabilized by pincer ligand hydrogenates
ethylene without a detectable induction period (Scheme
40c).250 At elevated temperatures Zn-silicates hydrogenate
propylene at 200 C (Scheme 40d). This material was
proposed to activate H2 on ZnO sites that forms transient
ZnH intermediates active in propene hydrogenation.493
Scheme 37. Reactivity of Surface Complexes towards

Ketones
species as shown in Scheme 38b.488 This reaction probably

involves -bond metathesis that is accompanied by -H transfer
to give the nal products.489
Analogous to the reactivity of the supported hydrides, Ta and
W permethyl supported species (Ta-1m, Ta-1b, and W-1m)
also react with alkanes to produce the corresponding metal
alkyl species and methane.144 (SiO)2TaH reacts with
cycloalkanes to yield the corresponding Ta cycloalkyl surface
complex and hydrogen. With cyclopentane, (SiO)2TaC5H9
Scheme 38. Methane Activation on (a) ZrSiO2-H-1 and (b) by TaSiO2-H-1 and (c) Reaction of Cyclopentane with TaSiO2-H-1
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for alkene metathesis catalysts that operate at room temperature.500505

Classical heterogeneous metathesis catalysts, prepared by
calcination of metal oxide precursors at high temperatures, are
typically activated rst at high temperature and then exposed to
olens. They are generally incompatible with functionalized
olens, with the exception of Re2O7/Al2O7 activated by
Me4Sn.8,506 With these ill-dened catalysts, only a small
fraction of the metal sites are active and the mode of formation
of the alkylidene remains unknown. The rst well-dened
heterogeneous metathesis catalyst was (SiO)Re(CtBu)(
CHtBu)(CH2tBu) (Re2m).301,302 Silica-supported alkene
metathesis catalysts belong to two distinct families, shown in
Scheme 41: (i) well-dened Mo, W, and Re alkylidene species
containing alkylidyne, oxo, or imido ligands, which initiate via
cross-metathesis with the existing bulky alkylidene ligand [refs
211, 287, 293, 297, 301, 302, 306311, 313, 316318, and
320] and (ii) well-dened alkene metathesis pre-catalysts that
form an alkylidene under reaction conditions. The precatalysts
contain Mo and W alkyl complexes supported on silica.287,320,323,507
Re2m shows high metathesis activity in comparison to
Re(CtBu)(CHtBu)(CH2tBu)2 in solution and classical
heterogeneous catalysts known at the time.301,302 Computational studies revealed that the high reactivity of this complex
resulted from the dissymmetry at the metal center that
decreases the energy barrier for coordination/decoordination
of the olen (the key elementary step of olen metathesis) and
destabilized the metallacyclobutane intermediates (Scheme
42).508511
This analysis extends to isoelectronic Mo and W imido/oxo
complexes and applies to the corresponding homogeneous
catalysts. 512518 In fact, (SiO)M(NAr)(CHtBu)
(CH2tBu) (M = Mo, W) display improved activity and stability
in comparison to Re2m and the related molecular systems.293,297 Replacement of the neopentyl groups by amide
and alkoxide ligands and tuning the imido ligand greatly
improved the overall catalytic performances, in particular by
avoiding the formation of olen-isomerization byproducts.211,307311,314 In addition, these silica-supported catalysts
are also compatible with functionalized alkenes such as ethyl
oleate; however, they have displayed poor performances in ring
closing metathesis.309
(SiO)W(O)(CH2tBu)3 probably generates the alkylidene
in situ by an -H abstraction process.287 While less active than
the well-dened tungsten imido alkylidene complex (
SiO)W(NAr)(CHtBu)(CH2tBu) (16,000 TON in propene
metathesis at 30 C after 24 h), (SiO)W(O)(CH2tBu)3
yields a more stable catalyst at high temperature, yielding
22 000 turnovers in 95 h for the self-metathesis of propene at
80 C.
The homogeneous oxo alkylidene W molecular complex
W(O)(CHtBu)(OHMT)2 was recently described,519 and
was used to prepare the corresponding silica-supported
analogue, (SiO)W(O)(CHtBu)(OHMT).316 In cis-4-nonene metathesis (SiO)W(O)(CHtBu)(OHMT) has a
turnover frequency at 3 min (TOF3 min) of 280 min1. It is
among the most active well-dened heterogeneous metathesis
catalysts,316 with activity far greater than the homogeneous
W(O)(CHtBu)(OHMT)2 precursor, which has TOF3 min =
5 min1 under the same reaction conditions. This large
dierence in activity is probably due to the presence of two
large aryloxy ligands in W(O)(CHtBu)(OHMT)2. Upon
Scheme 39. Hydrogenation of Benzene by Cp*ZrH2/AlS
Scheme 40. Transition Metal Hydrogenation Catalysts

Supported on Silica
4.2. Metathesis of Alkenes and Alkynes
4.2.1. Alkene Metathesis Using Group 67 SilicaSupported Catalysts. Alkene metathesis was discovered 60
years ago using both homogeneous and heterogeneous
catalysts.8,95,494497 Chauvin proposed that metallocarbenes
and metallacyclobutanes were the key reaction intermediates of
olen metathesis.498,499 This insight ultimately led to the
development of homogeneous well-dened alkylidene catalysts
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Scheme 41. Well-Dened Supported Alkene Metathesis Catalysts
(CHtBu)(X) with 13C-dilabeled ethylene results in the

formation of either the TBP or SP metallacyclobutane, and
their ratio allows the -donation of the X-ligand to be ranked
(Figure 15): the weaker -donor X-ligands favor the TBP over
Scheme 42. Elementary Steps in d0 Alkene Metathesis
grafting on silica one of these large groups is replaced by the

relatively small SiO group in (SiO)W(O)(CHtBu)
(OHMT). Larger aryloxy ligands give increased activity in
olen metathesis. Using the bulkier (SiO)W(O)(CHtBu)
(dAdPO), TOF3 min of 356 min1 can be reached in the selfmetathesis of cis-4-nonene.317 It also provides >75 000
turnovers in 1-hexene self-metathesis, when ethylene is vented
from the reaction.317 (SiO)W(O)(CHtBu)(OAr) catalysts
are active in ethyl oleate metathesis, in contrast to the classical
WO3/SiO2 catalyst. This result shows that silica-supported Woxo alkylidenes are compatible with functional groups and that
the incompatibility of WO3/SiO2 is probably related to the high
reaction temperatures necessary to form active sites. Replacing
the aryloxy ligand in (SiO)W(O)(CHtBu)(OHMT) by
an arylthiolate in (SiO)W(O)(CHtBu)(SHMT) improves
the catalytic activity in terminal olen metathesis. This is
probably due to a decrease in the stability of the metallacyclobutane as the strong -donor ArS ligand leads to a strong
electronic dessymetrisation at the W center.318
The improved activities and stabilities of the silica-supported
catalysts discussed above in comparison to their homogeneous
analogues originate from two factors: (i) site isolation that
prevents deactivation by bimolecular decomposition,520 (ii) the
surface siloxy group is a sterically small, weak -donor ligand
with electronic properties similar to OtBuF3.211 The sterics of
the surface siloxy ligand was evaluated by its buried volume521
using an isolated silanol on the (111) surface of -cristobalite.
The buried volume is roughly 20.6%, compared with 36.8% for
dAdPO.317 This result probably explains the lower activity of
the molecular precursor in the W oxo series discussed above.522
In the (SiO)W(NAr)(CHtBu)(X) series, the electronic
inuence of X ligands (X = OtBu, OtBuF3, OtBuF6, OtBuF9, and
OSi(OtBu)3) was evaluated in detail by assessing the TBP/SP
ratio of the corresponding metallacyclobutane and its relation
to the catalytic activity (TOF). Contacting (SiO)W(NAr)-
Figure 15. Formation and ratio of TBP/SP metallacyclobutanes for

(SiO)W(NAr)(CHtBu)(X) complexes, determined by 13C CPMAS
NMR.
the SP isomer (OtBuF9 < OtBuF6 < OtBuF3 < OSi(OtBu)3 <
OtBu).211,314,511,523,524 In this series, catalytic activity (TOF)
increases with decreasing -donation of the X-ligand.
A systematic investigation on the inuence of both the imido
and X ligands in (SiO)W(NAryl)(CHCMe2R)(X)
(Aryl = Ar, ArCl, ArCF3, and ArF5; X = OtBuF9, OtBuF6, OtBu,
OSi(OtBu)3, Me2Pyr; and R = Me or Ph) was recently
reported.314 The inuence of each member of the ligand set
was correlated to the TOF in cis-4-nonene self-metathesis using
multivariate linear regression analysis tools.525 The analysis
showed that the TOF of (SiO)W(NAryl)(CHCMe2R)(X) relates to the -donating character of the imido and X
ligands, evaluated by the NBO charge of the nitrogen atom in
ArylNH2 and the pKa of HX, respectively as well as the sterics
of the X ligand evaluated from the Sterimol B5 parameter (eq
1).314 This quantitative structureactivity relationship analysis
of the large series of well-dened heterogeneous catalysts
showed that high activity could be optimized by combination of
X and NAryl ligands of opposite electronic character and by a
simple and straightforward evaluation of the electronics and
sterics of the ligands from readily available parameters.314
TOF3min = 53.8 + 16.6(NBON,ArylNH2 /B5,HX )
+ 33.6(NBON,ArylNH2 /pK a,HX)
BG
(1)
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4.2.2. Alkene Metathesis Using Silica-Supported Ru

Alkylidenes. In contrast to Schrock-type alkylidene complexes, only couple of examples of well-dened silica-supported
Ru alkene metathesis catalysts have been reported. The silicasupported siloxide substituted Hoveyda-Grubbs catalysts Ru-4b
and Ru-5b (Scheme 12) are active in alkene metathesis. While
having a lower activity than homogeneous analogues, Ru-4b
and Ru-5b could be recycled more than 15 times in the ring
closing metathesis of diethyl diallyl malonate.298
4.2.3. Alkene Metathesis with Re and W on AluminaContaining Supports. Re2O7 supported on alumina is an
active heterogeneous catalysts for alkene metathesis that is
somewhat unusual because it is active at room temperature and
tolerant to functional groups when activated with alkyltin
compounds.526 In contrast to the well-dened silica supported
rhenium perhydrocarbyl discussed above (Re2m), rhenium
oxide complexes are inactive when supported on silica.527530
Active Re oxo-based catalysts are always supported on Lewis
acidic supports.531 For instance, chemisorption of methyltrioxorhenium (MTO) on acidic oxide supports leads to highly
active catalysts.358,378,404,532536 For CH3ReO3/-Al2O3 the
minor species (1015%) was proposed to be a reservoir of
highly active alkylidene species, a process shown in Scheme
43.377 While alkylidene intermediates have not yet been
Scheme 44. Proposed Formation of Tungsten Alkylidene

Species from Tungsten Hydride on Alumina in the Presence
of Ethylene
45a).541 The similarities between alkene and alkyne metathesis

led to similar mechanistic proposals. Alkyne metathesis involves
Scheme 45. (a) Early Example of Alkyne Metathesis; (b)
Proposed Mechanism and Representative Homogeneous
Catalysts; and (c) Single Site Supported Alkyne Metathesis
Catalysts
Scheme 43. Surface Species Obtained by Grafting CH3ReO3

on -Al2O3
spectroscopically identied, the exchange of the -methylene

ligand upon reaction with 13Clabeled olen is consistent with
this proposal.377,536 More recently, a similar -methylene
species was observed for Re2O7/-Al2O3 activated with
Me4Sn, suggesting the presence of similar active sites in both
systems.537 With other supports, it is not yet clear what are the
active sites, even if the presence of Lewis acid sites are critical
for activity.532,403,404
Passivation of the alumina surface with Me3Si groups in
CH3ReO3/Al2O3 results in an increase of the activity and the Zselectivity in the metathesis of propene into ethylene and 2butenes.535 These increases of performances have been related
to the change of adsorption properties of the supports, which
allow for a fast desorption of olens and hence the faster rate
and the observation of the kinetic Z-olenic products.
Dispersing ZnCl 2 on silicaalumina support prior to
CH3ReO3 grafting was shown to greatly enhance olen
metathesis activity.358 Chlorine atoms interacting with Re
centers have been proposed as key to the increase of activity.538
Tungsten hydride species supported on alumina catalyze
ethenolysis of 2-butenes into propene and the cross-metathesis
of isobutene and trans-2-butene aording propylene and
isopentene products (Scheme 44).539,540 The alkylidenes are
proposed to be formed by the reaction of tris-hydrides and
ethylene yielding the corresponding tris-ethyl intermediate,
which further undergoes -abstraction to form the W(
CHMe)(Et) species shown in Scheme 44.540
4.2.4. Alkyne Metathesis. WO3/SiO2 catalyzes the
disproportionation of 2-pentyne at 200450 C (Scheme
the [2 + 2] cycloaddition of a metal alkylidyne (A) and an

alkyne to form the metallocyclobutadiene (B) shown in
Scheme 45b.542 This mechanism is supported by the isolation
of stable metallocyclobutadienes and the dissociation of these
complexes into free alkyne and carbyne in solution (Scheme
45b).543,544 Numerous early transition metal carbyne complexes catalyze alkyne metathesis in solution, a few
representative catalysts are shown in Scheme 45b.543546
(SiO)Re(CtBu)(CHtBu)(CH2tBu) was the rst
reported well-dened alkyne metathesis catalyst (Scheme
45c). It catalyzes the disproportionation of 15 equiv of 2pentyne into an equilibrium mixture of 2-butyne, 2-pentyne,
and 3-hexyne within 20 min.301 (SiO)Mo(CEt)(N(tBu)Ar)2 (Mo-20m) catalyzes the metathesis of a variety of alkynes
with TOFs ranging from 0.30.05 molsub molcat1 s1 and
catalyst loadings of 4.00.2 mol % (25500 equiv of alkyne)
without the formation of undesirable oligomers.322 However,
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(Scheme 47c).268,275,277 As oxo complexes of early transition

metals tend to form O-bridged oligomeric structures, which
terminates the catalytic cycle, silica-supported oxo and imido
complexes were recently utilized as catalysts taking advantage of
site-isolation that prevents oligomerization. This strategy
aorded heterogeneous catalysts that outperform their
homogeneous counterparts by almost an order of magnitude
(Scheme 47d).268,275,277 Among the reactions studied are
imidation of aldehydes, ketones, and DMF with N-sulnylamines (Scheme 47e), and condensation of isocyanates or Nsulnylamines into carbodiimides or sulfurdiimines, respectively
(Scheme 47f).
the corresponding system grafted on silica partially dehydroxylated at 140200 C leads to unselective catalysts that catalyze
both alkyne metathesis and polymerization.547 This catalyst is
compatible with alkynes containing alkyl, aryl, benzoate,
thiophene, and methoxy substituents and can be recycled.
(SiO)W(CtBu)(OAr)2 (W-34m) is inactive in alkyne
metathesis at room temperature but becomes active at 80 C
with initial TOF of 0.32 molsub molW1 min1.324 The related
complex (SiO)W(CtBu)(CH2tBu)2 (W-33m) is inactive in
alkyne metathesis.323 In analogy to the example above, (
SiO)W2(NMe2)5 (W-2m) is also inactive in alkyne metathesis,
but its reaction with 5 equiv of tBuOH forms (SiO)W2
(NMe2)5n(OtBu)n (W-2m-OtBu) which equilibrates 4-nonyne
(50 equiv) in less than 30 min.158 However, control
experiments suggest that metathesis with this system probably
occurs in solution.
(SiO)Mo(N)(Py)(OSiMe3)(NMe2) (Mo-22m)548 catalyzes alkyne metathesis between 45 and 80 C with a sizable
induction period.325 This metal-nitrido complex probably reacts
with an alkyne to form the alkylidyne in situ. The addition of
B(C6F5)3 increases the initial rate of metathesis and reduces the
induction period observed in the absence of borane (Scheme
46). B(C6F5)3 assists the conversion of the MoN to the
4.4. Oligomerization of Alkenes
4.4.1. Ethylene Dimerization and Trimerization. High

surface area silica supports containing well-dened chloroalkylaluminum species are very ecient cocatalysts for the Nicatalyzed dimerization of ethylene, eq 2.552,553
Et2AlCl grafted onto silica reacts with nickel complexes to

dimerize ethylene in the presence of BiPh3 with moderate
selectivities to butenes; propylene dimerization gives dimers of
the monomer in good yields.553 Et2AlCl grafted onto silica
activates (n-Bu3P)2NiCl2 to form an ethylene dimerization
catalyst with TOFs up to 498,000 molC2H4 molNi1 h1.552 In
contrast, the corresponding silica-supported trialkylaluminum
species are not co-catalysts for this reaction.
Ta(III) species also catalyze the selective trimerization of
ethylene in solution.554,555 The surface Ta(V) complex Ta-4m
catalyzes the formation of 1-hexene with high selectivity and
TON up to 330.210,556 Analysis of the volatiles during the
trimerization reaction showed the formation of methane,
ethane, propylene and butane prior to formation of 1-hexene.
The presence of these compounds was rationalized by the
ethylene insertion, reductive elimination, and -hydride
elimination reactions shown in Scheme 48 to form the active
Ta(III) complex Ta-4m-X. Ta-4m-X oxidatively couples
ethylene to form a metallacyclopentane intermediate that
inserts one additional molecule of ethylene to form a
metallacycloheptane, similarly to the reactivity of Ta(III) in
solution.554,555 Ta-metallacycloheptane complexes are unstable
and undergo -hydride transfer to release 1-hexene, as shown in
Scheme 48.554,555
(SiO)3Ta also trimerizes ethylene to give 1-hexene,
though in this case polyethylene is also formed as a
byproduct.557 Detailed computational studies on this system
showed that trimerization is favored when a trigonal
bipyramidal geometry is enforced at the tantalum center
because this promotes -hydride elimination of the metallacycloheptane intermediate (Scheme 49). Distortion of this
species to square pyramidal environment opens a coordination
Scheme 46. Formation of Proposed Active Species in Alkyne

Metathesis Catalyzed by Silica-Supported Molybdenum
Nitride Mo-22m in the Presence of B(C6F5)3
alkylidyne ligand, probably by removing pyridine from the

metal center. The addition of Lewis acid to this catalyst results
in TOFs as high as 11.9 mol mol1 min1. A summary of the
catalytic activity of various alkyne metathesis catalysts is
compared in Table 7, below. The TOFs have been converted
to comparable units for ease of comparison.
4.3. Oxo/Imido Heterometathesis
Imidation of oxo complexes with isocyanates and N-sulnylamines is well-known in molecular chemistry549,550 and has
been used to probe the structure of surface oxo complexes of
Re,551 V,272,275 and Ta463 (Scheme 47a). Similarly, imido
complexes also participate in imido-transfer reactions with
aldehydes and other oxo-containing compounds, the stoichiometric reaction being demonstrated for supported V272,275 and
Ta268 imido complexes (Scheme 47b). Being combined, these
two transformations constitute a catalytic cycle referred to as
oxo/imido heterometathesis in analogy to olen metathesis
Table 7. Reactivity of Silica Supported Alkyne Metathesis Catalysts

complex
substrate
TON
Re2m
Mo-20mb
W-34ma
Mo-22mb
Mo-22m + 2 equiv B(C6F5)3b
MeCCEt
PhCCMe
MeCCEt
PhCCMe
PhCCMe
15
18
460
321
TOF (mol mol1 s1)[T (C)]
0.051
0.005
0.2
[22]
[24]
[80]
[45]
[110]
Reaction performed in gas phase. bReaction performed in solution.

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Scheme 47. (a) Imidation of Vanadium Surface Oxo

Complex; (b) Imido-Transfer Reaction of Tantalum Surface
Imido Complex; (c) Catalytic Cycle Proposed for Oxo/
Imido Heterometathesis Reactions; (d) Supported Catalysts
Used in Oxo/Imido Heterometathesis Reaction; (e)
Heterometathetical Imidation of Organic Carbonyls with NSulnylamines; and (f) Condensation of Isocyanates into
Carbodiimides and N-Sulnylamines into Sulfurdiimines
Scheme 48. (SiO)TaMe2Cl2-Catalyzed Trimerization of

Ethylene to form 1-Hexene
Scheme 49. Reaction of (SiO)3Ta and Ethylene:

Formation of Polyethylene vs 1-Hexene
butenes to form propylene.559 Deactivation of the WH3/Al2O3

catalyst is associated with ethylene insertions into Walkyl
bonds to form low density polyethylene that limits catalytic
turnover.560 More recently, an ETP catalyst was prepared by
treating (SiO)W(O)Cl3 with Me2Zn yielding the putative
reaction intermediate (SiO)W(O)Me3. This ETP catalyst
is able to reach 324 turnovers at 150 C.561
site for ethylene, which leads to olen insertion and polymeric

byproducts.
4.5. Direct Conversion of Ethylene to Propylene
The direct ethylene-to-propylene transformation (the ETP

reaction), originally discovered with Ni-doped mesoporous
silica (MCM41),558 is also catalyzed by WH3/Al2O3. This
system converts ethylene to propylene with >95% selectivity for
propylene at 150 C and 1 bar ethylene pressure in a
continuous ow reactor, giving TON of 1120 after 120 h on
stream.559 The proposed mechanism for the ETP reaction
catalyzed by WH3/Al2O3 is presented in Scheme 50. WH3/
Al2O3 enters the catalytic cycle by forming the W(CHMe)
(Et) alkylidene followed by insertion of ethylene and -H
elimination to give 1-butene and W(CHMe)(H). The latter
isomerizes 1-butene to 2-butenes, and any of the alkylidenes in
Scheme 50 can catalyze the metathesis of ethylene and 2-
4.6. Polymerization Reactions
The rst catalysts implemented for the polymerization of

ethylene were heterogeneous. The ZieglerNatta catalyst
contains TiCl4 supported on MgCl2 activated with AlR3
cocatalysts to generate active sites that polymerize ethylene.
The Phillips catalyst contains chromium sites supported on
silica and polymerizes ethylene in the absence of a cocatalyst.
Several groups described methods to access well-dened
heterogeneous catalysts inspired by the ZieglerNatta and
Phillips catalysts.
4.6.1. Single-Site Models of ZieglerNatta Type
Catalysts. The active sites in the ZieglerNatta catalyst are
BJ
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Scheme 50. Postulated Mechanism for the ETP on WH3/Al2O3
from the borate anion, a common decomposition pathway in

homogeneous catalysts,562 to form (SiO)Zr(Cp*)(C6F5)Me
and MeB(C6F5)2.
Grafting organometallic complexes on supports capable of
abstracting alkyl groups also provides active polymerization
catalysts with well-dened sites. As discussed above, the
reaction of M(CH2tBu)4 (M = Zr, Hf) with alumina
dehydroxylated at 500 C forms a mixture of surface species:
(AlO) 2 M(CH 2 tBu) 2 and [(AlO) 2 M(CH 2 tBu) + ][AlSCH2tBu].370,371 The Zr- and Hf-derivatives were shown
to have good activities in the polymerization of ethylene
without the need for a cocatalyst (eq 3), consistent with the
formation of zwitterionic [(AlO) 2 M(CH 2 tBu)][AlSCH2tBu].370,371,563 Similar results were obtained by grafting
Cp*ZrMe3 on silicaalumina or alumina.222
commonly proposed to be highly electrophilic cationic

organometallic species. This proposal is supported by extensive
studies on homogeneous olen polymerization catalysts. Welldened heterogeneous catalysts containing similar active sites
as proposed in the ZieglerNatta catalyst have been reported.
The polymerization properties are dependent on the support
and the polymerization conditions, as this aects the formation
and stability of the active site. Silica-supported catalysts
generally need a cocatalyst to form the active site. For example,
(SiO)ZrCp*Me2 is inactive in the polymerization of
ethylene. Adding B(C6F5)3 to (SiO)ZrCp*Me2 probably
forms the ion-pair [(SiO)ZrCp*Me][MeB(C6F5)3], which is
active in the polymerization of ethylene (Scheme 51a).222
Scheme 51. (a) Activation of (SiO)ZrCp*Me2 with
B(C6F5)3 to form [(SiO)ZrCp*Me][MeB(C6F5)3] and (b)
Deactivation Pathways Encountered with [(
SiO)ZrCp*Me][MeB(C6F5)3]
Complexes supported on sulfated metal oxides are also active

in ethylene polymerization.4,14,15,444,449,564 As discussed above,
the sulfated oxide support contains acidic OH functional groups
that eectively behave as weakly coordinating anions after
organometallic functionalization. In many cases the polyethylene generated with these catalysts cannot be extracted
from the heterogeneous particle, even at 140 C in 1,2,4trichlorobenzene.448,564 These results indicate that the polyethylene formed using these supported catalysts has ultrahigh
molecular weights.
4.6.2. Single-Site Models for the Phillips Catalyst. A
few years prior to the discovery of the ZieglerNatta catalyst
researchers at Phillips petroleum showed that silica containing
reduced chromium sites polymerize ethylene.565 The Phillips
precatalyst contains Cr(VI) sites, shown in Scheme 52, which
are prepared by incipient wetness impregnation of silica with an
aqueous solution of CrO3 or Cr(OAc)3 followed by calcination
at high temperatures (>400 C). High density polyethylene is
formed when the Cr(VI) sites are contacted with ethylene. This
catalyst is unique among ethylene polymerization catalysts
because it does not contain a preformed CrC bond and
polymerizes ethylene in the absence of an activator.
Though the active site of the Phillips catalyst is unknown, it
is formed in a complex series of redox events. It was shown that
ethylene reacts with Cr(VI) sites on silica to form aldehydes,
ketones, and mostly Cr(II) on the silica surface.566 Several
groups showed that isolated Cr(II) sites are present on the
silica surface after treatment with CO, a common model for the
Alternatively, cationic Zr-species supported on silica are

accessible by the reaction of [HNEt2Ph][(SiO)B(C6F5)3]
with Cp*ZrMe3 to form the [Cp*ZrMe2(NEt2Ph)][(SiO)B(C6F5)3],342 although this complex is unstable under
polymerization conditions.224 Silica supported Cp*TiMe3
catalysts were also reported, though in this case AlMe3
cocatalysts were used to form active sites.219 These highly
electrophilic Zr-species supported on silica are unstable under
polymerization conditions and react with the silica surface to
form inactive sites. For example, [(SiO)ZrCp*Me][MeB(C6F5)3] decomposes by two competitive processes shown in
Scheme 51b.223,342 Alkyl transfer to the silica surface forms
[(SiO)2ZrCp*][MeB(C6F5)3] and SiMe; these species
do not contain a ZrMe group and cannot polymerize
ethylene. Another decomposition process is C6F5 transfer
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-hydride elimination571 to form Cr-alkyl-hydride surface

species that can propagate polymer growth.
The ligandless Cr-silicates discussed above contain welldened sites in controlled oxidation states (see section 3.3,
Scheme 29).197,198,572574 However, (SiO)4Cr2 (Cr-6T) has
poor polymerization activity, which was completely suppressed
in the presence of 0.2 equiv of 4-picoline poison per chromium
site. Cr-6T also contains a small amount of Cr(III) sites
according to EPR spectroscopy, suggesting that Cr(III) sites
may be active in polymerization. Ethylene polymerization
experiments with (SiO)6Cr2 (Cr-6T-Ox, see section 3.4,
Scheme 35) produces a polymer with large dispersity = Mw/
Mn = 9.4 (with Mn = 5500 g mol1 and Mw = 52 000 g mol1)
that is typical for polyethylene produced with the Phillips
catalyst. This catalyst contains ca. 65% active sites by poisoning
studies with 4-methylpicoline. Monomeric Cr(III) containing
(SiO)3Cr (Cr-5T) also polymerizes ethylene with similar
activity and produces polyethylene with similar properties as
Cr-6T-Ox. Also similar to Cr-6T-Ox, roughly 60% of the sites
in Cr-5T are active in polymerization according to poisoning
studies with 4-methylpyridine.
The higher polymerization activity of Cr(III) sites compared
to Cr(II) containing materials is consistent with numerous
examples in homogeneous chemistry,575,576 and reports of
Cr(III) salts supported on silica.577,578
Cr-6T-Ox and Cr-5T have high concentrations of active sites
on the silica surface, and both initiate polymerization without a
noticeable induction period. Since the edge position of the
XANES spectra of Cr-6T-Ox and Cr-5T is not altered upon
exposure to ethylene, the oxidation state of the Cr-sites is
conserved after catalysis. The formation of the rst CrC bond
was proposed to occur by the heterolytic cleavage of the CH
bond of ethylene to form Si-(OH)-Cr-vinyl species shown
in Scheme 54. Propagation of the polymer chain occurs by
insertion polymerization, and termination is the microreverse of
initiation.
Scheme 52. Reactivity of Cr(VI) Sites in the Phillips Catalyst

with Ethylene and CO to form Cr(II) Reduced Sites
active Phillips catalyst.3,567,568 This has led to the general

assumption that the isolated Cr(II) sites shown in Scheme 52
are active in polymerization using this catalyst. The Phillips
catalyst contains only ca. 10% active sites,569 which has led to
signicant eorts to synthesize well-dened Cr-catalysts for the
polymerization of ethylene.
The Phillips catalyst likely contains organometallic intermediates, and initial well-dened studies used (SiO)2Cr(CH2tBu)2 and (SiO)2Cr(CHtBu) as models for active
species in this system (Scheme 53a). At low ethylene pressures
Scheme 53. (a) Formation of (SiO)2Cr(CHtBu) and Its
Reactivity with Ethylene and (b) Polymerization
Propagation Mechanism
Scheme 54. Proposed CH Activation Step to form a CrC

Bond in Well-Dened Cr(III) Silicates
(ca. 60 Torr) (SiO)2Cr(CH2tBu)2 does not initiate the

polymerization of ethylene. However, under these conditions
the putative (SiO)2Cr(CHtBu) catalyzes the formation of
high density polyethylene. Detailed kinetic studies of this
catalyst showed that the polymerization is rst-order in
chromium and follows pseudo rst-order behavior in ethylene.
In addition, polymerizations with ethylene-d4 gave a kinetic
isotope of k(C2H4)/k(C2D4) = 1.29 0.05. The small primary
kinetic isotope eect is inconsistent with an alkylidene
metallacycle mechanism since this would require a 1,3hydrogen migration in the chromacycle to regenerate the
alkylidene. However, this result is consistent with the olen
insertion propagation mechanism, shown in Scheme 53b.570
(SiO)2Cr(CHtBu) was proposed to initiate polymerization by [2 + 2] cycloaddition with ethylene to form the
chromacyclobutane (Scheme 53a). The latter can insert
ethylene to form expaned metallacycles that eventually undergo
This mechanism was investigated by DFT using the cluster

models described in section 3.2.1.1. Using the B3LYP
functional the heterolytic CH activation of ethylene has a
moderate barrier, and the overall thermodynamic driving force
of the reaction is the insertion of ethylene into the Cr-vinyl
bond to propagate polymerization.197 The insertion of ethylene
into the Cr-alkyl bond is lower than chain transfer by 10 kcal
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mol1 in the absence of ethylene and lower by 4 kcal mol1 in

the presence of coordinated ethylene.579
4.6.3. Supported Late Transition Metal Catalysts for
the Polymerization of Ethylene. (SiO)Ni(-diimine)
(CH2SiMe3) (Ni-3m) is inactive in the polymerization of
ethylene.246 Ni(II) olen polymerization catalysts are cationic
d8 square planar complexes containing an open coordination
site.580 In Ni-3m the nickel center is saturated and cannot
coordinate ethylene. Addition of gaseous BF3 to Ni-3m results
in the formation of the ion pair [Ni(-diimine)(CH2SiMe3)][(SiOBF3)] (Ni-3m-BF3) shown in Scheme 55a. Ni-3m-BF3
Scheme 56. (a) Polymerization of Methylmethacrylate, (b)

-Butyrolactone, (c) Styrene, and (d) Isoprene by Supported
Complexes
Scheme 55. (a) Formation of [Ni(diimine)(CH2SiMe3)][(SiOBF3)] and (b) Formation of

Ni-4SiO2
Scheme 57. Alkane Hydrogenolysis Catalysts
polymerizes ethylene with moderate activities (215 kgPE

molNi1 h1 bar1) that are lower than similar nickel complexes
supported on alkylaluminum doped silica,581,582 or nickel
complexes supported on alkylaluminum doped MgCl2.583 The
reaction of (SiO)B(C6F5)2 with [N-phenyl-2-(phenylimino)propanamidato- 2 -N,N]( 1 -benzyl)-(trimethylphosphine)nickel(II) (Ni-4)584 forms the cationic nickel complex Ni-4SiO2
supported on silica shown in Scheme 55b.344 Ni-4SiO2
polymerizes ethylene with similar activities as homogeneous
equivalents. The polyethylene produced by Ni-4SiO2 has a
rather low dispersity = Mw/Mn = 2.2, indicating that the
active species in Ni-4SiO2 acts as a single-site catalyst.
4.6.5. Polymerization of Other Substrates. Ln[N(SiMe3)2]3 (Ln = La, Nd, Sm) supported on partially
dehydroxylated silica are catalysts for the polymerization of
methyl methacrylate (Scheme 56a).173,183 These catalysts
produce isotactic methyl methacrylate polymers with narrow
polydispersities. Ln(BH4)3 (Ln = La, Nd) supported on
partially dehydroxylated silica catalyze the ring-opening
polymerization of -butyrolactone to give isotactic polylactones
(Scheme 56b).585 Organocalcium reagents grafted onto silica
polymerize styrene to give low-molecular weight syndiotactic
polystyrene (Scheme 56c).586 Monophosphacyclopentadienyl
bis(tetramethylaluminate) lanthanide complexes and Ln(AlR4)3
supported on high surface area SBA15 and MCM48 are active
in the polymerization of isoprene to give cis-1,4-polyisoprene
(Scheme 56d).236,237
linear and branched alkanes, with the exception of ethane, to

form mixtures of methane and ethane as nal products (see
Scheme 58a for the hydrogenolysis of propane).132,139,456,460,461,486,587 Overall, comparing the catalytic
properties of Zr, Hf, Ta, and W hydrides supported on silica
alumina shows that the catalysts follow the trend in activity of
Zr > Hf > Ta > W and that Ta and W-hydrides are also able to
catalyze the hydrogenolysis of ethane.
The methane to ethane ratio depends on the initial alkane.
The mechanism shown in Scheme 58b,c involves activation via
-bond metathesis of CH3CH2R with MHx to form M
CH2CH2R species that undergo -alkyl transfer to form
M(CH2CH2)(R) species. This elementary step of carbon
carbon cleavage is consistent with the nal ethane/methane
4.7. Alkane Homologation Processes and Related

Reactions
4.7.1. Alkane Hydrogenolysis. The supported metal

hydrides shown in Scheme 57 catalyze the low temperature
hydrogenolysis of alkanes. In particular, group 4 metal hydrides
(Ti, Zr and Hf, Scheme 57a) catalyze the hydrogenolysis of
BM
Chemical Reviews
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suggest that CH bond activation corresponds occurs via a bond metathesis,487 which is easier on dihydride than
monohydride surface species (Scheme 58c).458
Hydrogenolysis of alkanes is also observed in the presence of
H2 with Zr hydrides supported on alumina459 or aminemodied SBA15 (Scheme 57c,d).590,591 In this study the Zrdihydride linked through [N,O]-chelating surface ligands was
proposed to be more active than the analogous system linked
via [N,N]-ligands.
(SiO)2TaHx (Scheme 57b) also catalyze the hydrogenolysis of alkanes, including ethane in contrast to group 4
metals.592 In this case methane is the nal product for acyclic
alkanes. (SiO) 2TaHx also cleave the CC bond of
cycloalkanes to yield acyclic and cyclic products. These results
indicate that the hydrogenolysis mechanism must dier from
that of supported group 4 hydrides. The proposed mechanism
for (SiO)2TaHx with alkanes is shown in Scheme 59a. The
Scheme 58. Hydrogenolysis of Alkanes on Supported Metal

Hydrides
Scheme 59. (a) Proposed Mechanism of Alkane

Hydrogenolysis Catalyzed by Silica-Supported Ta Hydrides
and (b) The Case of Cyclic Alkanes
key step of carboncarbon cleavage is an -alkyl transfer, which

corresponds to the microreverse step of alkyl insertion to the
TaC bond.593,594 The -alkyl transfer mechanism would
explain why all acyclic alkanes are converted to methane.
Computational studies suggest that the (SiO)2TaH3 are the
active species and that the rate-determining step is the -alkyl
transfer step.595,596 More recent studies suggest that -alkyl
transfer may also operate in the hydrogenolysis of higher
alkanes.597 For cyclic alkanes the structure of the products
suggest that a key step is -H abstraction followed via
retrocyclization and metathesis like reaction (Scheme 59b).490
ratio of 1:1 for the hydrogenolysis of propane. The observation

of methane to ethane ratio close to 1:1 in the hydrogenolysis of
butane shows however that -alkyl transfer from M-butyl and
M-sec-butyl intermediates are equally probable (Scheme
58d).405,406 This mechanism is also consistent with the
observation that cyclopentane and cyclohexane do not undergo
hydrogenolysis because -alkyl transfer requires a syn-coplanar
arrangement of the MC-C and CC-C bonds (Scheme
58e).
DFT calculations on cluster or extended models also agree
with the mechanism in Scheme 58.456,588,589 These studies
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4.7.2. Alkane Metathesis. Alkane metathesis is a reaction

that disproportionates an alkane into its lower and higher
homologues. The reverse reaction (called alkane cross-metathesis) is also possible, in which larger and smaller alkanes
comproportionate, yielding alkanes of intermediate size. This
reaction was discovered by using heterogeneous dehydrogenation/hydrogenation and alkene metathesis catalysts in
tandem.598 The tandem catalysis concept has also been used
to develop homogeneous systems that catalyze alkane metathesis.599 Alkane metathesis is also catalyzed by well-dened
group 5 and 6 supported metal-hydrides (Scheme 60). These
heterogeneous catalysts are multifunctional because they
perform dehydrogenation/hydrogenation and metathesis steps
at a single metal site.
Scheme 61. (a) Ta Hydride on Zr Doped Silica and (b)

Cross Metathesis of Ethane and Toluene
mediates metathesis, albeit with much lower TON (<40). Ta1b and W-1m and their methyl methylene derivatives Ta-1b150C were shown to be ecient catalyst precursors for alkane
metathesis, giving TON = 49 for Ta and TON = 120 for
W.144,150,605 The tungsten catalysts are typically more reactive
and more robust than those of tantalum. Ta-1b and W-1m
disproportionate linear alkanes,466 as well as catalyze the ring
opening metathesis of cyclooctane.561 Finally, silica-supported
WOCl4 activated by ZnMe2 also mediates the metathesis of
cyclooctane at 150 C, similar to other W-based catalysts.561
The proposed alkane metathesis mechanism466,606 is based
on the following evidence: alkenes are the primary products of
the reaction from ow kinetic studies,607 linear alkanes (Cn) are
transformed primarily into Cn+1 and Cn1, and the active metal
sites must be able to accommodate three anionic alkyl ligands.
These observations are consistent with a mechanism in which
CC bonds are formed and broken by alkene metathesis,
mediated by alkylidene hydride intermediates shown in Scheme
62.
In the proposed mechanism, tantalum hydride TaH-1
reacts with propane to form a tantalum propyl species. H
elimination from the propyl ligand, gives a Ta alkylidene
hydride intermediate. A series of alkane dehydrogenation and
alkene metathesis steps then complete the cycle. The alkylidene
hydride is multifunctional, able to perform both alkane
dehydrogenation and alkene metathesis, as shown in Scheme
62. The Cn+1 selectivity arises from the preferred formation of
1,3-disubstituted metallacyclobutanes (which give only Cn+1)
over 1,2-disubstituted metallacyclobutanes (Scheme 62).
Computational studies have shown that direct -bond metathesis between MR and alkane CC bonds is unlikely.595
Tantalum hydrides TaSiO2-H-1 and TaSiO2-H-3 can convert a
mixture of alkene and H2 into lower and higher alkanes. The
mechanism of this transformation is probably similar to that of
alkane/alkene metathesis.300
(SiO)3ZrH and (SiO)2ZrH2 do not show any metathesis reactivity with propane. However, under supercritical
conditions, silicaalumina supported zirconium hydrides
catalyze the metathesis of propane to form branched rather
than linear alkanes.608 Dialkyl species (SiO)2Zr(CH2tBu)2
(Zr-1b) gives similar rates and selectivities under the same
reaction conditions. The active site is probably the bis-hydride
(SiO)2ZrH2 (ZrASA-H-2). The proposed mechanism involves
the reaction of ZrASA-H-2 with alkanes to produce dialkyl Zr
species, [Zr(C3H7)2]. This species undergoes -alkyl transfer to
produce [Zr(C3H7) (Me)(C2H4)] (Scheme 63). This intermediate can then produce a variety of dierent products. For
instance, insertion of ethylene into the propyl ligand gives npentane. Alternatively, transfer of the -H of the propyl ligand
to the ethylene ligand (by -H transfer/insertion) makes
Scheme 60. Representative Examples of Single-Site Metal

Hydrides, Alkyls, Alkylidenes, and Alkylidyne that Are
Catalysts for Alkane Metathesis
The rst multifunctional alkane metathesis catalysts were (

SiO)2TaHx (TaSiO2-H-x where x = 1 or 3).600 (SiO)2TaHx
converts propane at 150200 C into methane, ethane, and
butanes, along with smaller amounts C5 and C6 isomers, 60
turnovers are obtained after 120 h. Titration showed that ca.
50% of Ta sites are active in catalysis. The inactive species
probably interact with adjacent siloxane bridges. Similar
performances were found for alumina or silicaalumina
supported Ta hydrides373 or on Ta hydrides prepared on Zrdoped silica support464 (Scheme 61a). (SiO)2TaHx (TaSiO2H-x where x = 1 or 3) also catalyzes the cross metathesis of
ethane and toluene (Scheme 61b).601
The low activity of the silica-supported W hydrides is
attributed to the low amounts of tungsten hydride on the
surface and the formation of W clusters discussed in section 3.3.
However, the silicaalumina and alumina supported analogues
show improved performance, with the alumina-supported
tungsten hydride reaching 120 TON in 120 h.373,374 In the
case of alumina, the active surface species is (AlSO)W(O)H3
(WAl2O3-H-3).
Silica-supported neopentyl neopentylidene complexes of
groups 5 and 7 (Ta-12m, W-19m, and Re2m) also catalyze
propane metathesis (Scheme 57c).225,602604 W-19m also
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Scheme 62. Proposed Mechanism of Propane Metathesis Catalyzed by Supported Ta Hydrides
Scheme 63. Disproportionation of Alkanes on Zr Alkyls
Scheme 64. (a) Overall Reaction of Nonoxidative Coupling

of Methane and (b) Proposed Mechanism
propylene. Subsequent insertion of propylene into the methyl

ligand would produce 2,2-dimethylpropane. The insertion of
propylene into metal alkyl bonds occurs selectively to produce
the primary MC bond, explaining this catalysts preference for
branched rather than linear alkanes.
4.7.3. Cross-Metathesis of Methane and Higher
Alkanes. The cross-metathesis of methane and higher alkanes
is slightly endoergic, and requires a large excess of methane
(1000 equiv) to convert propane to ethane. Tantalum hydrides
TaSiO2-H-1 and TaSiO2-H-3 catalyze this reaction at 250 C
with high selectivity but low rate.609
4.7.4. Nonoxidative Methane Coupling. Silica-supported Ta hydrides and alumina-supported W hydrides also
catalyze the coupling of two methane into ethane and H2
(Scheme 64a).488 WAl2O3-H-3 is the most active catalyst, giving
35 turnovers in 10 d. Since this is a highly endothermic

reaction, the conversions can be increased by using a
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membrane reactor to displace the equilibrium. 610 The

mechanism of this reaction probably involves similar steps to
other alkane metathesis reactions (Scheme 64b). The TaH
reacts with methane to make a TaCH3 species. -H
elimination from the CH3 ligand produces a Ta methylidene
hydride. The hydride of this intermediate reacts with additional
methane to produce hydrogen gas and a Ta methyl
methylidene. The methyl ligand then migrates to the
methylidene to produce a Ta-CH2CH3 species. This ethyl
species reacts with more methane to give ethane and restart the
cycle.
The proposed mechanism of the dehydrogenation of alkanes

by metal ions on oxide surfaces involves heterolytic CH bond
activation across an MO site, as illustrated in Scheme 65c for
Cr(III)O sites.5,606 This mechanism requires an active site to
contain a coordination site for the CH bond cleavage and an
additional site for the -hydride transfer step. Cr-5T catalyzes
the dehydrogenation of propane with an initial TOF of 10 h1
that decreases to 2.8 h1 after 2 h on stream.574 This catalyst is
72% selective for propene with the balance being methane and
ethene. DFT calculations suggest that heterolytic CH bond
activation from Cr-5T to form the CrPr species shown in
Scheme 65c is the rate-limiting step. The CrPr intermediate
-H eliminates to form the CrH that releases propene and H2
to complete the cycle. These calculations also suggest that the
formation of methane and ethene (cracking) results from alkyl elimination from the CrPr intermediate (Scheme 65c).
Other isolated metal sites such as VO3+, Ga3+, In3+, FeOx,
Zn2+, Fe2+, and Co2+ catalyze alkane dehydrogenation.5 (
SiO)V(O)(Mes)2 (V-5m) catalyzes the dehydrogenation of
propane with 8090% propene selectivity and 1020%
conversion at 500 C.278 The TOF for this catalyst was
approximately 0.5 h1. Well-dened Fe(II) sites in Fe-3m550C catalyze dehydrogenation at 550 C with TOF = 1.01.4
h1 and 99% selectivity toward propene (after subtraction of
uncatalyzed thermal cracking).152 Calcination of metal nitrates
such as Zn(NO3)2493 and Co(NO3)2612 dispersed on silica
yields isolated sites that catalyze the dehydrogenation of
propane. These materials dehydrogenate propane at 550 C
with TOF of 0.8 for Zn and 0.61.7 h1 and Co; both catalysts
display very high selectivities for propene ranging from 91
95%. DFT calculations suggested that CH bond activation by
these systems probably occurs via heterolytic CH bond
activation, similar to the mechanism shown in Scheme 65c for
Cr(III) sites.
4.8. Dehydrogenation of Alkanes
The availability of inexpensive propane derived from shale

gas611 is causing a surge in research in the dehydrogenation of
propane.5 The two heterogeneous catalysts currently in use
industrially are the Oleex catalyst, which contains aluminasupported Sn-doped Pt particles, and the CATOFIN catalyst,
which relies on chromium sites on Al2O3.5 The dehydrogenation of alkanes is thermodynamically unfavorable5 and requires
high temperatures (550650 C) to shift the equilibrium
toward propene and H2 (Scheme 65a), but can be carried with
a broad range of supported metal ions besides Cr(III)/Al2O3
(Scheme 65b). These harsh conditions lead to cracking side
reactions that cleave CC bonds and ultimately lead to coke
formation. Coke covers the surface and deactivates the catalyst.
Scheme 65. (a) Propane Dehydrogenation Reaction; (b)
Single-Site Catalysts that Have Been Investigated; and (c)
Proposed Mechanism of Propane Dehydrogenation for Cr5Ta
4.9. Epoxidation of Alkenes
Propylene oxide is produced in industry by the oxidation of

propylene with alkyl hydroperoxydes or more recently
hydrogen peroxide (Scheme 66a). While the process utilizing
alkyl hydroperoxydes relies on TiCl4 supported on silica, the
one using hydrogen peroxide is enabled by Ti-silicalite.9 The
catalysts based on TiCl4/SiO2 are still poorly understood,
despite recent advances.203 Silasesquioxane soluble models
suggest tripodal Ti sites as the most catalytically active (Scheme
66b).613 Ti(CH2tBu)4 grafted on SiO2480 followed by
hydrolysis or calcination formed isolated Ti sites that were
active in epoxidation of cyclohexene in the presence of organic
hydroperoxides ROOH or hydrogen peroxide.614 With H2O2,
the catalyst performance was improved by passivation of the
silica surface with Me3Si groups.451 These reports induced
numerous eorts to obtain better epoxidation catalysts.
Ti-6b catalyzes the epoxidation of terminal and internal
olens and allylic alcohols in the presence of dry tertbutylhydroperoxide (TBHP, Table 8, entry 1).155,185 The
reaction is highly selective and can proceed in neat substrates.
Ti-6b epoxidizes propylene as well.185 In contrast, contacting
Ti(OiPr)4 with silicone nanospheres containing silanol, TMS,
and methyl surface groups avoids aggregated TiOTi
linkages and forms predominantly site-isolated titanium centers
(Ti-26t, Scheme 66b).615 Soluble Ti-26t is active in cyclohexene epoxidation with H2O2, cumene hydroperoxide (CHP),
or TBHP in toluene at 65 C (Table 8, entry 2).
A similar mechanism is expected for other metal ions.

BQ
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Scheme 66. (a) Catalytic Epoxidation of Alkenes and (b) Epoxidation Catalysts
Table 8. Comparison of Selected Supported Epoxidation Catalysts in Cyclohexene Epoxidation

Entry
1
2
3
4
5
6
7
8
9
10
Cat.
Ti-6b
Ti-26t
Ti-10m
Ti-27tf
Ti-20m
Ta-9b
Ta-14tf
Mo-23m
Fe-8b/t
Fe-13m
Solvent
Decane
Toluene
Toluene
CH3CN
Octane
CH3CN
CH3CN
CH2Cl2
CH3CN
CH3CN
[O]
TBHP
CHP
CHP
H2O2
TBHP
H2O2
H2O2
TBHP
H2O2
H2O2
T (C)
Time (h)
50
65
65
65
60
65
65
40
25
60
16
2
1
2
8
3
2
2
1
1
Ca or Yb
a
98
24.5b
e
15.3a
54a
7.3a
7.4b
99.5a
71.5b
7.3a
Sel.c
TONd
Ref
100
>98
e
20.0
e
80g
98.4
98.9
45
24
62.5
176
643
116
633
132
83
957
64.8
2.6
185
615
193
617
263
266
617
326
199
243
a
Total conversion of peroxide (%). bEpoxide yield based on peroxide (%). cSelectivity for epoxidation product (%). dTON = mol epoxidation
product/mol metal. eno tabulated data available. fRcap = n-Bu. gepoxide + diol.
catalysts, cumene hydroperoxide (CHP) gives high activity and

selectivity to the cyclohexene oxide in toluene at 65 C (Table
8, entry 3). The catalytic activity of materials prepared by
grafting molecular precursors with low Ti/Si ratio (Ti-8, Ti-10)
Ti-8, 9, and 10 on Aerosil silica, MCM41 or SBA15 partially

dehydroxylated at 200 C form mostly monografted tetrahedral
Ti species Ti-8m, 9m, and 10m shown in Scheme 66.193 While
H2O2 is ineective in the epoxidation of cyclohexene with these
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Chemical Reviews
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Scheme 67. Capping Strategy for Improved Epoxidation Catalysts
Scheme 68. Proposed Epoxidation Mechanisms with Ta and Ti Catalysts
cyclohexene epoxidation at 60 C in dry octane using CHP or

TBHP as oxidant (Table 8, entry 5).263 The reaction pseudo
rst order rate constants and hot ltration experiments indicate
that no deactivation, leaching or product inhibition took place.
Activity of a related complex Ti-22m was lower than Ti-20m,
demonstrating that the identity of the supporting calixarene
ligand inuences the catalytic properties of the material.261 The
calixarene approach was extended to include Ta(V) complexes
that upon grafting were proposed to give mono- and bipodal
surface species, such as Ta-9b (Table 8, entry 6).265,266
Comparing Ta and Ti calixarene systems, Ta complexes
provide higher selectivity to cyclohexene oxide when using
H2O2 than respective Ti catalysts, although the Ta system gave
high amounts of cyclohexane-1,2-diol. Capping of surface
silanols with octanol allowed us to reduce this secondary
hydrolysis pathway.266
Ta-3m and Ta-3b, obtained by grafting of (iPrO)2Ta[OSi(OtBu)3]3 on SBA15130, enabled epoxidation of cyclohexene
in good selectivities with organic peroxides (94% with CHP
and 70% with TBHP) and poor selectivity with H2O2 (36%) in
acetonitrile at 65 C.196 Exposure of Ta-3m and Ta-3b to air at
200 C followed by capping with (N,N-dimethylamino)trialkylsilane was proposed to give surface sites Ta-14t that
featured improved catalytic performance with H2O2 (Table 8,
entry 7).450 While capping has a modest eect on activity, the
selectivity for epoxide was improved to 98%, by comparison
with only ca. 32% with the surface unmodied catalyst. After 6
h, the epoxide yields produced by capped catalyst Ta-14t were
ca. 5 times higher than with the unmodied catalyst,
emphasizing that hydrophobic surface capping suppressed
poisoning of the active Ta sites by water. It was also proposed
that the siloxy group on Ta remains within its coordination
sphere during the catalysis.450,619 This strategy to modify
surface properties for improved catalysis was further extended
to include related Ta-15t species with trimethylsilyl, -germyl,
and -stannyl groups.620 Ta-15t has higher selectivity for
cyclohexene oxide and 1,2-cyclohexene diol and slower rates
of H2O2 decomposition than the unmodied catalyst. However,
Ta-15t has a slower rates of cyclohexene epoxidation with
H2O2 after 10 h compared to the unmodied catalyst.620 Ge
was improved, with turnover numbers up to 2,000.193 Ligandfree catalysts were prepared by calcination of Ti-8m, 9m, and
10m and showed reduced activity, possibly due to migration of
the titanium centers into the support, making the catalytic sites
less accessible.193 In order to evaluate the eect of a dimeric Ti
precursor, [(tBuO)2Ti{-O2Si[OSi(OtBu)3]2}]2 was grafted on
SBA15130 to give Ti-11m epoxidation catalyst.195 Ti-11m has
similar activity and selectivity for cyclohexene epoxidation with
organic hydroperoxides as Ti-8m, 9m, and 10m. Several
parameters were suggested to determine high catalytic activity
of Ti catalysts including more Lewis acidic Ti sites formed from
Si-rich molecular compounds, tetrahedral Ti(IV) sites, suppressed nucleation to octahedral TiO2 and high dispersion of Ti
sites.193,195 Ti[OGe(iPr)3]4 on SBA15120 (Ti-12m) was
compared to the siloxide-only precursors for cyclohexene
oxidation with TBHP and found to produce 23 times higher
TONs after 9h under identical conditions.191 The activity and
selectivity of Ti-8m and Ti-11m in epoxidation using H2O2 can
be improved by capping surface OH groups with Me2N
SiMe2(R) (R = Me, n-Bu, or n-octyl, Scheme 67).616
When compared with uncapped Ti materials, species on
modied surfaces such as Ti-27t exhibit up to 58% selectivity
for cyclohexene oxide over the undesired allylic oxidation
products (Table 8, entry 4).616,617 Treating Ti-10m capped
with Me2NSiMe2(R) at 200 C under O2 exposes free Ti
OH.194 Modication of these titanols with phenols and
carboxylic acids results in 10 to 50% higher conversions and
selectivity of 1-octene epoxidation with TBHP or H2O2.194
Isolated Ti centers as well as oligomerized Ti species (TiO2
nanoclusters) could be prepared by grafting Ti(OiPr)4 on
mesoporous aluminophosphate (AlPO) supports that contain
reactive surface AlOH and POH groups.618 The catalytic
activity and selectivity of cyclohexene epoxidation with TiAlPO is slightly lower than that of Ti-SBA15 material with
comparable Ti loadings and using TBHP; additionally, Ti-AlPO
materials form more allylic oxidation products.618
The isolation of Ti sites could also be obtained by grafting
molecular precursors containing a large calixarene ligand. The
corresponding grafted complex Ti-20m displays a rigid
pseudotetrahedral geometry, and TONs up to 633 for the
BS
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Scheme 69. (a) Industrial Synthesis of Adipic Acid; (b) Catalytically Active Species and Their Activity in Cycloalkane
Oxidation; (c) Deperoxidation with M = Ti, R = tBu, H and M = Zr, Hf, R = tBu; (d) Benzylic Oxidation of Alkyl Aromatics;
and (e) Methane Oxidation
entry 9).199 Fe-13m does not catalyze cyclohexene epoxidation

with TBHP, it slowly forms cyclohexene oxide with H2O2 in
acetonitrile with 7.3% conversion after 1 h and 24% selectivity
(Table 8, entry 10).243,621 The poor selectivity is indicative of
competing radical oxidation pathways.
and Si capped catalysts performed better in terms of rate and

selectivity than Sn modied catalysts. Though the activity with
Ta was modest, these results suggested that Ta(V) surface
species are more water-tolerant than the more active Ti(IV)
catalysts. It was proposed that oxygen transfer from Ti and Ta
sites occurs via an electrophilic transfer to the alkene from a
peroxide intermediate and that side products are formed via
radical manifolds (Scheme 68).195,450,619
Mo-23m catalyzes olen epoxidation with TBHP in reuxing
DCM, and has higher activities than (tBuO)3Mo(N).326
However, Mo-23m deactivates during recycling due to 15%
Mo leaching in each cycle (Table 8, entry 8). Mo-3m and W6m have activities and selectivities below 10% in cyclohexene
epoxidation with TBHP (toluene, 65 C); W-6m is more active
than Mo-3m.284 These materials deactivate relatively fast,
presumably due to the formation of water and alcohol side
products. In contrast to Ti materials described above,
calcination does not have a strong eect on the performances
of Mo-3m and W-6m.284
Grafting Fe(OSi(OtBu)3)3(TMEDA) on SBA15190 followed
by calcination at 300 C for 2h gives Fe-8b/t species that
epoxidizes cyclohexene with H2O2 in acetonitrile at room
temperature giving TON value of ca. 65 after 1 h (Table 8,
4.10. Oxidation and Deperoxidation of Alkanes
The conversion of cyclohexane to cyclohexanol via an

intermediate cyclohexyl hydroperoxide is a key step in
industrial process to make adipic acid shown in Scheme
69a.131 Homogeneous chromium-complexes catalyze this
reaction to give cyclohexanol and cyclohexanone at higher
than 100% selectivity, indicating that activation of the solvent
(cyclohexane) by cyclohexyl hydroperoxide occurs.
Isolated Fe(III) silicates oxidize cyclohexane to cyclohexanol
in the presence of H2O2 at 60 C with high selectivity.199,200
Longer reaction times lead to decreased selectivity due to
competing cyclohexanone formation (Scheme 69b).199 Isolated
Fe(III) silicates convert adamantane to a mixture of tertiary and
secondary alcohols in a 3.1/1 ratio, as well as 2-adamantonone
with an overall TON of 15. The ratio of tertiary to secondary
alcohol products suggests that a nonradical oxidation pathway
occurs in this reaction.199
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Chemical Reviews
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conditions and give TON values similar to the Ti system

(Table 9, entries 68).186 In contrast to homogeneous
catalysts, the observed selectivities with Ti, Zr, Hf and Ta
supported catalysts does not show evidence for cyclohexane
oxidation by cyclohexyl hydroperoxide according to a pathway
analogous to that presented in Scheme 69b.131,186
Co-3m enables selective benzylic oxidation of alkyl aromatics
with TBHP in acetonitrile solution at 80 C (Scheme 69d),
presumably via a radical mechanism.245 Oxidation of ethylbenzene with Co-3m is rapid in the rst hour (TOF up to 582)
slowing down over the course of the reaction likely due to the
catalyst poisoning with H2O.
Single-site vanadium silicates (SiO)3VO, prepared from
well-dened (SiO)V(O)(OR)2 grafted species (R = Si(OtBu)3 or tBu)279 catalyze the oxidation of methane to
formaldehyde by molecular oxygen at 400 C yielding ca. 2.4%
formaldehyde at 815% methane conversion with a space-time
yield of 5.84 kgald kgcat1 h1 (Scheme 69e).279
Well-dened heterogeneous catalysts of the general type (

SiO)3MOR (M = Ti, Zr, Hf; R = H, tBu) (Scheme 69c) also
catalyze this reaction.131 (SiO)3MOtBu surface species show
activity in the deperoxidation of cyclohexyl peroxide in the
order Ti > Zr > Hf. (SiO)3TiOtBu reaches full conversion in
9 h with substrate/metal ratio =260.131 (SiO)3TiOH and (
SiO)TiNp3 (Ti-1m) show similar conversion vs time proles
and turn over numbers as compared to (SiO)3TiOtBu,
indicating that (SiO)3 TiOH and (SiO)TiNp 3 are
converted to catalytically active species (Table 9, entries 1
5).131
Table 9. Comparison of the Activities and Selectivities of
Silica-Supported Single-Site Catalysts for the
Deperoxidation of Cyclohexyl Hydroperoxide at 84 C131,186
entry
catalyst
S/Ca
time
(h)
conv.
(%)
1
2
3
4
5
6
7
8
(SiO)3HfOtBu
(SiO)3ZrOtBu
(SiO)3TiOtBu
(SiO)3TiNp3 + O2
(SiO)3TiOH
(SiO)Ta(OMe)4
(SiO)2Ta(OMe)3
(SiO)3Ta(OMe)2
260
350
260
312
252
270
250
240
6
6
6
6
6
6
9
8
30
40
88
77
87
88
66
88
sel.b
one/olc
4.11. Other Selected Catalytic Transformations

85
79
81
87
87
60
4.11.1. Hydroamination. Silylamides of Y, La, and Nd on

SBA15500 catalyze intramolecular hydroamination/cyclization
of 2,2-dimethyl-4-pentene-1-amine in benzene at elevated
temperatures.172 A mixture of Y-1m and Y-1b achieves high
rates with 5.7% catalyst loading cleanly converting the amine
substrate in <10 min (Scheme 70a). The catalytic activity is lost
after a third catalyst recycling, presumably due to product
inhibition.
4.11.2. Hydrosilylation. Related lanthanides were earlier
shown to catalyze hydrosilylation of terminal olens, although
the catalytic activity and linear/branched selectivity of
supported species was comparable and in some cases inferior
to performance of the molecular lanthanide precursors.171 Rh4m also catalyzes the hydrosilylation reactivity giving high
yields at 100 C with TOF up to 160 (Scheme 70b).214
0.7
0.84
0.72
1.5
1.3
0.9
a
Substrate/catalyst ratio. bSelectivity to cyclohexanone and cyclohexanol based on consumed cyclohexyl hydroperoxide. cCyclohexanone/cyclohexanol ratio.
Leaching of Ti is signicant (up to 30%), though hotltration tests showed that the desorbed species were not
responsible for the catalytic activity. In contrast, silicasupported alkoxo-tantalum complexes (SiO)nTa(OR)5-n (n
= 13) are stable toward leaching under identical reaction
Scheme 70. Selected Catalytic Transformations and Respective Catalysts
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Figure 16. Templated formation of mesostructured hybrid organo-silica materials (ad), left; idealized regular distribution of organic moieties at the
silica surface and a representation of periodic mesoporous materials (right).
4.11.3. Other Reactions. Nb-1m is a catalyst in the

cycloaddition of CO2 and propylene oxide to propylene
carbonate at 60 C and 10 bar (Scheme 70c).206 Nb-1m
shows decreased activity in consecutive catalytic runs, which
was attributed to Nb leaching as well as restructuring of Nb
ligand sphere via chlorine loss.
A combination of V-9b with an immobilized lipase catalyst
enables dynamic kinetic resolution of a wide variety of racemic
alcohols with vinyl acetate at 35 C through 1,3-transposition of
the hydroxy group (Scheme 70d).280 The catalytic performance
of V-9b is improved compared to its molecular vanadium
precursor. Nearly quantitative conversion and enantioselectivity
was observed when the mixture of these cocatalysts was
recycled.
Cobalt surface species prepared by direct oxidation of grafted
complexes on basic (MgO and TiO2) and acidic (Y-Zeolite,
AlPO, and SBA15) supports exhibit activity in photochemical
water oxidation with a sacricial oxidant and a Ru sensitizer.
The activity is superior than that of a Co surface atom of a
Co3O4 nanoparticle (Scheme 70e).622 No anticipated correlation between the catalytic rates and the oxygen atom anities
of the supports was observed.
5. EMERGING FIELDS
5.1. Well-Dened Catalysts through Grafting on Advanced
Functional Materials
Tailoring supports has become an intense eld of research. One

approach is the incorporation of polyoxometallate clusters onto
silica, which results in the formation of surface silanols with
increased acidity.623628 Alternatively, an exchange of surface
silanols for amine functionalities enables grafting of metal
complexes.591,629631 Another approach is the installation of an
organic ligand onto the surface of a support.632 A recent
strategy includes the controlled incorporation of organic ligands
into oxide (usually silica) matrixes through the hydrolysis of
organosilicates in the presence of structure-directing agent
(SDA). The organosilane precursor contains hydrophobic and
hydrophilic fragments that align with the SDA micelle during
hydrolysis and silica condensation (Figure 16a).633 This
method produces predominantly tripodal silicon surface species
as deduced from the 29Si solid-state NMR studies. Removal of
the structure-directing agent from the mesopores of the thusformed hybrid silica material is achieved by Soxhlet extraction
(Figure 16b). Importantly, SDA strategy allows for a narrow
distribution of organic ligands dispersed in the pore structure of
the silica matrix due to the random distribution of organosilane
moieties in the micellar structure prior to hydrolysis. This is in
contrast to conventional postsynthetic modication of porous
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Scheme 71. Well-Dened Organometallic Catalysts on Hybrid Organo-Silica Materials
Figure 17. Templated formation of periodic mesoporous organosilicas (left) and selected catalysts.
materials discussed above, MOF and COF supports allow the

use of functional groups/ligands other than surface OH groups.
Below, we highlight recent selected examples of well-dened
heterogeneous catalysts on MOFs and COFs with the emphasis
on controlled postsynthetic modication. MOFs are derived
from an inorganic cluster, called secondary building unit, and an
organic ligand strut (Figure 18a). MOFs containing the
dicarboxylate of 2,2-bipyridyl (bPy) with UiO topology can
be metalated with Ir or Pd complexes. These materials
exhibited activities for CH borylation of arenes, orthosilylation of benzyl silyl ethers or dehydrogenation of
substituted cyclohexenones to phenols, respectively.654,655
The salicylaldimine ligand incorporated into the MOF network
binds Fe and Co complexes (Figure 18b) that are ecient
catalysts for olen hydrogenation.656 BINAP-derived MOFs
bind Ru and Rh complexes that enantioselectively hydrogenate
-keto esters and also catalyze conjugate addition reactions.657
Postsynthetic modication of the aniline-containing walls a
MOF with pyridine 2-carboxaldehyde Ni complex (Py-2-CHO
NiCl2) installs the supporting ligand along with the bound
metal species. (Figure 18c).658 This material is active in the
dimerization of ethylene to give 1-butene in the presence of
Et2AlCl.
Microporous organic polymer (POP) supports are amorphous with nonuniform pores.659664 POPs can contain
hydroxyl groups depending on the type of monomer used in
the synthesis of the material. POPs containing catecholate
groups react with Ta(V) trialkyls present to form Ta(V) trialkyl
species shown in Scheme 72.660 These materials are active in
hydrogenation of cyclohexene and toluene.
silica that often leads to inhomogeneous densities of surface

species.67
These hybrid materials combine the stability of oxides and
the modularity of ligand design.633 Hybrid materials were
designed to include selective CH functionalization,634 alkyne
semihydrogenation,635 CO2 hydrogenation,636 and alkene
metathesis catalysts that often have activities greater than
their homogeneous analogues (Scheme 71).604,637 In the case
of Ru metathesis catalysts, the pivotal role of the organic tether
on the catalytic performance was revealed by selecting a exible
linker to allow for a stabilizing RuOS interaction (Scheme
71d), in analogy to the eect found in molecular HoveydaGrubbs metathesis catalyst.
Periodic mesoporous organosilicas (PMOs) are organic
inorganic materials with ordered mesoporous structure, can
analogously be made via a templated sol gel of appropriate
organosilica precursors as described above to give materials
with organic moieties inside the pore walls (Figure 17).638,639
In this case, the organic moiety is located in the pore wall of the
material and can be used to graft/anchor metal sites.
The incorporation of a chiral BINAP linker into the PMO
walls enabled Ru-based asymmetric hydrogenation and transfer
hydrogenation of 1,3-dicarbonyl substrates with high activity
and enantioselectivity and with no destruction of the PMO
material under high hydrogen pressures.640 Examples of
molecularly dened heterogeneous catalysts based on PMOtype supports involve materials with bipyridine-based linkers
that provided active catalysts for CH borylation (Figure 17)
with turn over numbers up to 728.641643
Metalorganic frameworks (MOFs) and covalent organic
frameworks (COFs) contain periodic crystalline microporous
networks, and have attracted substantial attention for the
preparation of heterogeneous catalysts, as was thoroughly
described in recent reviews.644653 Similar to the hybrid
5.2. Molecular Approach Beyond Well-Dened

Heterogeneous Catalysts
This review described developments in surface organometallic

chemistry over the past ca. 15 years. This approach is broadly
applicable beyond the preparation of well-dened so-called
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in the nal property in a range of applications. Applications of

the molecular approach in microelectronics, where dosage and
location of dopants at the nm scale, will become increasingly
important as devices become smaller and smaller.66,695,696
These are only a few examples of where controlled surface
chemistry is beginning to impact many dierent technological
areas. We expect that application of the molecular approach to
controlled surface chemistry, coupled with the application of
more sensitive and sophisticated characterization techniques,
will continue to grow by leaps and bounds in the following
years.
Scheme 72. Cat-Ta-POP Heterogeneous Catalyst
6. CONCLUSIONS
Industrial heterogeneous catalysts are usually developed and
optimized by empirical approaches due to the complexity of
these materials. As shown in this review, the continuing
development of molecular chemistry and the advancement of
tools to characterize complex materials has allowed the
preparation of heterogeneous catalysts containing well-dened
active sites to emerge as an alternative and powerful strategy to
empirical methods. Understanding the surface chemistry of the
oxide support is a critical step to choose an adequate molecular
precursor for grafting because the surface determines the
binding of the metal site and promotes or hinders side
reactions. Generally, molecular precursors react with a surface
oxide OH group by protonolysis of a MX group, where X is
an appropriately reactive anionic ligand. In a few cases
alternative grafting pathways were uncovered, in particular for
molecular precursors containing multiply bonded ligands.
SiO 2700 is a nearly ideal support for well-dened
heterogeneous catalysts because it contains a low coverage of
mostly isolated silanols (ca. 0.8 OH nm2). On this support
most grafting reactions occur by protonolysis of an MX group
single-site catalysts discussed above. For example, posttreatment of well-dened surface species under pressures of
H2 can lead to the controlled growth of clusters and
nanoparticles with improved reactivity compared to supported
nanoparticles prepared from classical methods. The choice of
the molecular precursor is often essential to the resulting
particle size and the interface between the support and the
particle.168,213,381 The surge of research in electro- and
photocatalysis is also converging toward similar molecular
approaches where control of the structures of surface species is
critical for optimal catalytic behavior.424,429,665680 Outside of
catalysis, the benets of controlling the structures of surface
sites are rapidly becoming apparent in materials used in imaging
technologies.88,681683 The molecular approach is also nding
broad acceptance in the design and implementation of
nanocrystals684693 and functionalized nanoparticles or composites,448,694 where the control of surface chemistry has impacts
Figure 18. Idealized molecular representations of fragments of (a) bpy-Ir-UiO, (b) sal-Fe/Co-UiO, and (c) one-pot postsynthetic condensation to
Ni@(Fe)-MIL-10-NH2.
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ization techniques progress and provide deeper structural
in the metal precursor to form monografted surface species.

However, the surface species on SiO2700 have slightly dierent
local environments because silica surfaces are amorphous. Some
metal sites are in close contact with siloxane bridges. These
siloxane bridges can open in the presence of electrophilic metal
centers to form additional SiOM bonds, a process
encountered in several examples throughout this review.
The linkage of the metal complex to a siloxy group of the
partially dehydroxylated silica support increases the electrophilicity of the metal center, opens its coordination sphere, and
isolates the complex to prevent bimolecular side reactions that
can occur in solution. Each of these eects impacts the activity,
selectivity, and stability of the well-dened catalyst. A
combination of these eects also explain why silica supported
systems can have greater activity and stability than closely
related homogeneous equivalents.
Introduction of a second siloxy ligand would presumably lead
to even more electrophilic metal centers. The most common
method to synthesize surface species containing (SiO)2MLn
fragments is the reaction of LnM(X)2 with silica partially
dehydroxylated at lower temperature, typically SiO2200.
Though mass balance analysis of the grafting step is consistent
with the formation of (SiO)2MLn species, several studies
point to the presence of mixtures on the surface, indicating that
alternative strategies to obtain such species need to be
developed.
The surface chemistry of alumina is more complex than silica,
and several types of surface species are often obtained.
However, alumina provides access to unique structures that
are not accessible on silica. Besides hydroxyl, alumina contains
surface AlIIIO sites that react with CH4, H2 and activate CH
bonds of organometallics to form AlCH2M species. These
Lewis acidic Al-sites can also abstract alkyl groups from
organometallic reagents to form cationic surface complexes.
Silicaalumina is more complex because this material has
properties in-between pure silica and pure alumina.
Alternative oxides and more exotic supports have not yet
been as extensively studied as silica, alumina, or silicaalumina.
Of these supports, sulfated alumina and sulfated zirconia are a
promising class of materials that react with organometallic
complexes to form weak surface ion pairs. The weakly
coordinating surface ions are very electrophilic and are highly
active in the hydrogenation of arenes and in the polymerization
of ethylene.
Transforming well-dened sites on oxides into coordinatively
unsaturated species are accessible by a variety of posttreatments. In most cases these reactive species are not readily
accessible in molecular chemistry. For example, highly
electrophilic low-coordinate metal hydrides were obtained by
the reaction of group 46 (SiO)MRn with H2. These metal
hydrides activate CH bonds and catalyze hydrogenolysis and
metathesis of alkanes at low temperatures. Another example is
the thermal treatment of supported metal siloxides and related
derivatives, which provide well-dened high- or low-oxidation
state isolated metal sites as models of industrial catalysts.
Ti(IV) and Ta(V) isolated sites provide active epoxidation
catalysts are models for the Shell epoxidation catalyst. Cr(II)
and Cr(III) isolated sites revealed that the active sites in the
Philipps ethylene polymerization catalysts are likely Cr(III),
and initiate polymerization by a CH bond activation step.
The advances in functionalization of surfaces over the past 15
years have been possible because of the development of
advanced spectroscopic and modeling techniques. As character-
information about surface sites, the scope of the molecular

approach will likely broaden to more complex materials. The
scope of applications using a molecular approach is virtually
limitless, providing that well-dened metal sites can inuence
the behavior of the material.
ASSOCIATED CONTENT
S Supporting Information
*
The Supporting Information is available free of charge on the

ACS Publications website at DOI: 10.1021/acs.chemrev.5b00373.
Complete lists of authors for the references containing
more than 10 authors (PDF)
AUTHOR INFORMATION
Corresponding Author
*E-mail: ccoperet@inorg.chem.ethz.ch.
Notes
The authors declare no competing nancial interest.

Biographies
Christophe Coperet was trained in chemistry and chemical engineering in CPE Lyon and then undertook a Ph.D. in chemistry at Purdue
University (USA) under the supervision of Prof. Negishi (1996). After
a postdoctoral stay in the group of Prof. Sharpless, he joined C2P2 (at
the time LCOMS) as a CNRS researcher in 1998 and was promoted
CNRS Research Director in 2008. Since 2010, he is Professor at the
Department of Chemistry at ETH Zurich. His research interest lies at
the interface of molecular, material, and surface chemistry with
applications in catalysis, energy, imaging, and microelectronics, and his
work relies on the combination of advanced spectroscopic methods
like surface enhanced NMR spectroscopy and computational
chemistry.
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University, where he was a Department of Energy Predoctoral Fellow

in the laboratory of Prof. Jack Norton. In 2014, he moved to ETH
Zurich, and he is currently a Marie Curie Postdoctoral Fellow in the
Laboratory of Prof. C. Coperet.
Aleix Comas-Vives graduated from the Autonomous University of

Barcelona in 2004 and obtained a Ph.D. in theoretical and
computational chemistry in 2009. After a postdoctoral position in
the group of Prof. Timo Jacob in 2012 he joined the group of Prof.
Christophe Coperet at ETH Zurich. Since 2014, he is Ambizione
Research Fellow from the Swiss National Foundation and develops ab
initio approaches to provide further understanding at atomistic level of
the structure and reactivity of complex systems such as single-site
catalysts, oxide materials, and metallic nanoparticles.
Alexey Fedorov completed his undergraduate studies in chemistry at

Saint Petersburg State University (Russia) in 2005 working with Prof.
Mikhail A. Kuznetsov (SPbSU) and Heinz Heimgartner (University of
Zurich). He then moved to the ETH Zurich (Switzerland), where he
received a Ph.D. under the mentorship of Prof. Peter Chen in 2010.
After a Swiss National Foundation postdoctoral fellowship at the
California Institute of Technology with Prof. Robert H. Grubbs
(20102012), he returned to the ETH to work with Prof. Christophe
Coperet, where he currently carries out his Habilitation supported by
the Holcim Stiftung and ETH Zurich.
Matthew P. Conley received his B.S. in chemistry from the University

of Illinois at Chicago (2004) and his Ph.D. in inorganic chemistry at
the University of Chicago under the supervision of Prof. Richard F.
Jordan (2008). He was a postdoctoral research fellow at the ICIQ in
Tarragona, Spain from 2008 to 2011 with Prof. Javier de Mendoza and
at ETH Zurich with Prof. Christophe Coperet from 2011 to 2015. He
is now an assistant professor of chemistry at the University of
California, Riverside.
Victor Mougel earned his M.S. degree in chemistry at Ecole Normale

Superieure de Lyon, France in 2009. In 2012, he received a Ph.D. in
inorganic chemistry from the University of Grenoble in France, where
he studied the design, synthesis, reactivity, and magnetic applications
of polynuclear uranium assemblies under the guidance of Marinella
Mazzanti. He joined the Coperet group at ETH Zurich as a ETHMarie Curie fellow in 2012, where his research has focused on the
development of well-dened silica supported alkene metathesis
catalysts. He has joined the College de France in Paris as a CNRS
Deven Estes received a B.S. in chemistry from the University of

Oklahoma in 2009. In 2014 he earned his Ph.D. from Columbia
associate researcher from January 2016.

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Pavel A. Zhizhko graduated from Lomonosov Moscow State

University in 2008 and defended his Ph.D. in Chemistry at A. N.
Nesmeyanov Institute of Organoelement Compounds (Moscow,
Russia) in the group of D. N. Zarubin in 2012. He currently holds a
researcher position in the same group and makes regular visits to the
group of Prof. C. Coperet at ETH Zurich. His research interests lie in
the eld of organometallic and coordination chemistry, in particular on
surfaces, in relation to catalytic reactions such as the imido-transfer
reactions.
ACKNOWLEDGMENTS
We are grateful to the Marie-Curie Fellowship program, SNF,
and ETHZ for nancial support. A.C.-V. thanks the SNF for
nancial support (Ambizione Project PZ00P2_148059). We
also thank Profs. M. Delferro, T. J. Marks, J. Sauer, C. Chizallet,
and P. Raybaud for sending us coordinates of some of the
systems to make suitable gures.
Haruki Nagae was born in 1987 in Tokushima, Japan. He studied at

Osaka University where he obtained his Ph.D. in chemistry in 2015
under the supervision of Prof. Kazushi Mashima. His doctoral research
focused on CH bond activation mediated early transition metals, and
he visited ETH Zurich to develop new approaches in surface
chemistry. In 2015, he joined Mitsui Chemicals Inc. as a researcher.
DEDICATION
This review is dedicated to the memory of Yu. I. Yermakov
(19351986), one of the pioneers of the eld, on the occasion
of the 80th anniversary of his birth.
ABBREVIATION LIST
SupportT subscript indicates temperature of dehydroxylation
of the support (e.g., SiO2700)
AS
Degussa Aerosil-200
SG
silica gel
IR
infrared spectroscopy
Raman
Raman spectroscopy
UVvis
UV and visible region spectroscopy
EA
elemental analysis
MB
mass balance analysis
TGA
thermogravimetric analysis
NMR
nuclear magnetic resonance spectroscopy
EPR
electron paramagnetic resonance spectroscopy
Magn
Magnetic Moment and Magnetic Susceptibility
Measurements
XPS
X-ray photoelectron spectroscopy
XANES
X-ray absorption near edge structure spectroscopy
EXAFS
extended X-ray absorption ne structure spectroscopy
EDX
energy-dispersive X-ray spectroscopy
Ar
2,6-iPr2C6H3
Ar
3,5-Me2C6H3
ArCl
2,6-Cl2C6H3
ArCF3
2-CF3C6H4
ArF5
C6F5
Ad
1-adamantyl
Mes
2,4,6-Me3C6H2
tBuF3
CMe2(CF3)
tBuF6
CMe(CF3)2
tBuF9
C(CF3)3
Pyr
pyrrolyl
Me2Pyr
2,5-dimethylpyrrolyl
dppz
3,5-diphenylpyrazolyl
dtpz
3,5-di-t-butylpyrazolyl
HMTO
2,6-Mes2C6H3O
HMTS
2,6-Mes2C6H3S
dAdPO
2,6-Ad2-4-MeC6H2O
DME
dimethoxyethane
DMF
N,N-dimethylformamide
Francisco Nunez-Zarur was born in Cartagena de Indias, Colombia.

He rst studied chemistry at the University of Cartagena, and then
moved to Barcelona, Spain to join the group of Prof. Mariona Sodupe
in the Autonomous University of Barcelona, where he received a M.Sc.
degree in Theoretical and Computational Chemistry in 2009 and a
Ph.D. degree in 2012. Dr. Nunez-Zarur then worked in the group of
Prof. Christophe Coperet at ETH Zurich, Switzerland. In May 2015 he
went back to Colombia with a fellowship sponsored by the Colombia
government (Colciencias) and joined the group of Prof. Albeiro
Restrepo at the University of Antioquia, where he is studying
homogeneous and heterogeneous catalysis through a computational
approach.
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Chemical Reviews
TMEDA
COD
COT
acac
fod
Review
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N,N,N,N-tetramethylethylenediamine
1,5-cyclooctadiene
1,3,5,7-cyclooctatetraene
acetylacetonate
1,1,1,2,2,3,3-heptauoro-7,7-dimethyl-4,6-octanedione
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3.4. Stoichiometric Reactivity and Activation of

Received: June 26, 2015

dened active sites. One powerful approach, known as surface

Table 1. Methods of Characterization and Chemical Information on Surface Sites

mass balance analysis (MB)

homogeneous molecular models

examples of information provided by each method

surface area, porosity

specic polymorph of the support and level of crystallinity

2. CONCEPTS, DEFINITIONS, TOOLS, AND PRACTICAL

analysis, and/or mass spectrometry, to name a few common

2.1. Concepts and Denitions

An important step to synthesize heterogeneous catalysts using a

2.2. Toolbox of Characterization Methods

A combination of techniques that describes the support and

ne structure spectroscopy (EXAFS) provide information

Raman, resonance Raman) are critical to understand the

In addition, the surface sites are often present as a distribution

of primary particles and surface properties of the solid

2.3. Practical Aspects

the two arms of the ask, as shown in Figure 2b. A solution of

compatible with their use in glovebox, grafting can be

Figure 3. Calcination, dehydroxylation and grafting on a pressed pellet of a support.

the, now MSOH depleted, oxide surface. The reaction of the

shown in Figure 3. After pressing a sample of the support in air

3.2. Structure of Surface Species Resulting from Grafting of

3.2.1. Silica-Supported Well-Dened Metal Sites.

3. DESCRIPTION OF THE SURFACE CHEMISTRY ON

To restate, the key concept in SOMC is treating oxide surfaces

SiOH nm2. An alternative amorphous silica surface model

3.2.1.2. Grafting Molecular Precursors on Silica and

we also provide a summary of characterization methods for

Scheme 2. Grafting of MLnXx Molecular Precursor on (a)

species described below follow this general reaction path

Table 2. Well-Dened Silica-Supported Surface Complexes

Scheme 3. Grafting of Zr(NMe2)4 on SiO2700

Scheme 5. Grafting and Further Evolution of [Ti(OiPr)4]2 on SiO2500

dimeric [Ta(OMe)5]2 reacts with SiO2700 to form the

quantity of surface silanols present on the partially dehydroxylated silica support.

(tBuO)3SiO. This is also supported by the dierence in

M(NR2)n, and M(OR)n, fewer MCln salts have been supported

Scheme 7. Grafting [Re(CO)3OH]4 onto SiO2

Scheme 6. Interaction of Zr(OtBu)4 and Zr(CH2tBu)4 with

kinetic dierence in reactivity, the thermodynamic product is

Scheme 8. Grafting Nd(AlMe4)3 onto Silica

Metal Complexes Containing N- and P-Donor Ligands.

Scheme 9. Grafting (a) Ta(CHtBu)(CH2tBu)3, (b) Re(

Ir(acac)3254 generate the corresponding grafted species by

In sharp contrast, the reaction of Os(CHtBu)2(CH2tBu)2

Scheme 10. Identied Species upon Grafting of W(

Scheme 12. Grafting Ruthenium Alkylidene Complexes on

(Scheme 10). This result shows the degree of complexity that

yields (SiO)M(E)(X)2. As in the other cases mentioned

and Table 2u, entry 1).319,320 Heteroleptic alkylidyne

Scheme 11. syn and anti Isomers of (SiO)Re(CtBu)(

Scheme 14. Reaction of Grignard Reagents with (a) Silanol

NMR spectroscopy shows that the J(CH) coupling constant

The reaction of alkylaluminums with high surface area

SBA15500 forms a complex mixture of aluminum species

Scheme 15. Reaction of (a) AlEt3 and (b) GaMe3 with

Scheme 17. Reaction of [Et2AlCl]2 with SBA15500

The reaction of B(C6F5)3 with partially dehydroxylated silica