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Katalis Homogen

Katalis Homogen

Katalis

Katalis

Jenis katalis

Katalis homogen adalah senyawa yang ada dalam fase yang sama (gas atau cair) sebagai reaktan , sedangkan katalis heterogen <dak berada dalam fase yang sama dengan reaktan .

Katalisis asam, katalis organologam, dan katalisis enzima<k adalah contoh katalis homogen . Paling sering , katalis homogen melibatkan pengenalan katalis fase cair ke dalam larutan reaktan . Dalam kasus tersebut, asam dan basa sering katalis sangat efek<f, karena mereka dapat mempercepat reaksi dengan mempengaruhi polarisasi ikatan .

Keuntungan dari katalis homogen adalah bahwa katalis lebih cepat bercampur ke dalam campuran reaksi , yang memungkinkan <ngkat yang sangat <nggi dari interaksi antara molekul katalis dan reaktan . Namun , berbeda dengan katalisis heterogen , katalis homogen sering <dak bisa kembali ke bentuk awal ke<ka reaksi telah berjalan sampai selesai .

Organometallic

According to RSC

According to RSC
According to RSC

According to ACS

According to ACS
According to ACS

Noble-Prize Winners in Works Related to OM

Grignard & Saba<er (Grignard reagents) in 1912. Ziegler & NaRa (Ziegler-NaRa catalyst) in 1963. Fisher & Wilkinson (Sandwich complexes) in

1973.

Sharpless & Noyori (Hydrogena<on & Oxida<on) in 2001. Chauvin & Grubbs & Schrock (Alkene Meathesis) in 2005. Heck & Negishi & Suzuki ( Pd catalyze C-C bond forma<on) in 2010.

Trans Effect

In inorganic chemistry, the trans effect is the labiliza<on (making unstable) of ligands that are trans to certain other ligands, which can thus be regarded as trans-direc<ng ligands. It is aRributed to electronic effects and it is most notable in square planar complexes, although it can also be observed for octahedral complexes. The cis effect is most o`en observed in octahedral transi<on metal complexes.

ELECTRON COUNTING

Basis of Electron Coun<ng

Basis of Electron Coun<ng

Importance of Electron Coun<ng

Importance of Electron Coun<ng

Coun<ng Electron

Method 1: The ionic (charged) model Method 2: The covalent (neutral) model

Method 1: The ionic (charged) model

Pada metode ini melibatkan ligan sebagai pendonor pasangan electron ke logam. Untuk menentukan jumlah total electron, kita harus menghitung juga muatan se<ap ligand dan menentukan <ngkat atau bilangan oksidasi formal dari atom pusat.

Contoh : dikarbonil kloro pentahapto siklopentadienil besi (II) (η5-

C 5 H 5 )Fe(CO) 2 Cl

η5-C H - mendonorkan 3 pasang e-, CO mendonorkan 2 elektron ( karena terdapat 2 CO maka dikali 2), Fe(II) = [Ar]4s 0 3d 6 jadi mendonorkan 6 elektron , sehingga jika dijumlahkan :

Fe (II)

η5-C 5 H 5 - : 6 e-

2(CO) Cl -

Total eletron : 18 elektron

5

5

: 6 e-

: 4 e- : 2 e-

Method 2: The covalent (neutral) model

Pada metode ini kita akan menggunakan jumlah electron yang akan didonasikan oleh ligand tetapi dalam keadaan netral . Pada ligan anorganik sederhana, jumlah electron yang didonasikan sama dengan muatan nega<fnya sebagai ion bebeas . Misalnya Cl donor 1 e- ( muatan ion bebas -1), O donor 2 e- ( muatan ion bebeas -2), N donor 3 e- ( muatan ion bebas -3). Pada metode ini kita <dak memerlukan penentuan bilangan oksidasi dari atom pusat. Contoh : dikarbonil kloro pentahapto siklopentadienil besi (II) (η5-C 5 H 5 )Fe(CO) 2 Cl Fe mendonorkan 8 e- sesuai konfigurasi elektronnya, η5-C H mendonorkan 5 e- ( kita memper<mbangan ligan ini sebagai ligan netral ), CO mendonorkan 2 e-, dan Cl mendonorkan 1 e- ( sebagai spesies netral )

η5-C 5 H 5 : 5 e-

2(CO)

Total

5

5

Fe

: 8 e-

: 4 e- : 1 e- = 18 e-

Cl

Ligan dengan donasi elektronnya

Ligan dengan donasi elektronnya

TRANSITION METALS ORGANOMETALLICS

A transi:on metal is one which forms one or more stable ions which have incompletely filled d orbitals .

Transition vs Main Elements

The physical and chemical properties of transition metals differ from main group metals (s-block) by the following:

are hard and have high densities. have high melting and boiling points. form compounds which are often paramagnetic. show variable oxidation states. form coloured ions and compounds. form compounds with profound catalytic activity. form stable complexes.

Transi:on Metals Overview

Transi:on Metals Overview

Early Transi:on Metals Groups 3, 4

Strongly electrophilic (Strongly bounds to high electronega<ve ligands that stablize higher oxida<on states such as F-, O2-, =O). Few redox reac<ons (excep<on: Ti) Usually electron deficient complexes (less than 18e). Polar and very reac<ve M-C bonds (to alkyl and aryl). Few d-electrons:

– preference for "hard" -donors – weak complexa<on of π-acceptors

Early Transi:on Metals Groups 3,4

Typical catalysis in Polymerization

Early Transi:on Metals Groups 3,4 Typical catalysis in Polymerization

"Middle" Transi:on Metals Groups 5-7

Many accessible oxida<on states. Mostly electron precise (18e). Ligands strongly bound.

Strong, not very reac<ve M-C bonds.

Preference for -donor/ -acceptor (such as CO and NO).

combina<ons

"Middle" Transi:on Metals Groups

5-7

Typical catalysis: Alkene and alkyne metathesis

"Middle" Transi:on Metals Groups 5-7 Typical catalysis: Alkene and alkyne metathesis

Late Transi<on Metals Groups 8 (and

9)

Many accessible oxida<on states. Mostly 18e or 16e (16e common for square- planar complexes). Easy ligand associa<on/dissocia<on Weak, not very reac<ve M-C bonds (weak orbitals overlap with low bond polarity). Even weaker, reac<ve M-O/M-N bonds

Preference for s-donor/weak p-acceptor ligands

( phosphines)

Late Transi<on Metals Groups 8 (and 9)

Typical catalysis: C-C bond forma<on

Late Transi<on Metals Groups 8 (and 9) Typical catalysis: C-C bond forma<on

Transi<on Metals

Transi<on Metals

1st row:

o`en unpaired electrons (High spin state). different spin states (HS/LS) accessible highest oxida<on states not very stable 2nd/3rd row:

nearly always "closed shell" Highest oxida<on states fairly stable 2nd row o`en more reac<ve than 3rd

Nomenclature

The mode of aRachment of the donor ligand is described by deno<ng the number of atoms (together with posi<ons if necessary) aRached to the metal atom by ηn . e.g. pentacarbonyl (η1-methyl)manganese(I),

MnMe(CO)5

(η1-allyl) pentacarbonylmanganese(I), Mn (η1-

CH2CH=CH2)(CO)5

(η3–allyl ) tetracarbonylmanganese(I), Mn (CO)4(η3-

C3H5)

tricarbonyl (η5-cyclopentadienyl)manganese(I), Mn (CO)3(η5-C5H5)

Metal Carbonyls (Bonding)

Metal Carbonyls (Bonding)

Evidence of Back-bonding

Note that an empty orbital in the ligand (LUMO) is used in the bonding (an an<- bonding orbital). Using the an<-bonding orbitals in the ligand decreases the strength of the bond (Bond Order in MO theory). Many techniques can read the weakness of the ligand bonding (X-ray - IR – NMR – Mass Spectrometry).

Metal Phosphines

Ter<ary phosphines, PR3, are important because they cons<tute one of the few series of ligands in which altera<on of electronic and steric proper<es can be managed in a systema<c and predictable way over a very wide range by varying R groups. Other effects can be introduced such as chelate and macrocyclic effects. Also, chirality can be introduced by having chiral phosphine ligands. They also stabilize wide variety of ligands of interest as their phosphine complexes (R3P) nM−L.

Bonding in Metal Phosphines

Bonding in Metal Phosphines

Electronic Effects of Phosphines

Electronic Effects of Phosphines

Controlling The Space Around The Metal

Controlling The Space Around The Metal

Correla:on of Cone Angles & Reac:on

Correla:on of Cone Angles & Reac:on

Mono-dentate Phosphines

Mono-dentate Phosphines

We can increase the bulkness around the metal by replacing the phosphine ligand without affec<ng the electronic factor PMe 3 (118 0 ) and PEt 2 Ph (133 0 ) We can change the electronic factor around the metal by replacing the phosphine ligand without affec<ng the bulkness . P(C 6 H 4 -4-CH 3 ) 3 , PPh 3 , P(C 6 H 4 -4-CN) 3 (145 0 )

Tolman plot of Electronic Parameter and Cone Angle

Tolman plot of Electronic Parameter and Cone Angle

Hydrido Complexes

Hydrido Complexes

METAL AMINE

METAL AMINE

Metal Alkenes (Bonding)

Metal Alkenes (Bonding)

Ligand Assosia<on & Dissocia<on

Ligand Assosia<on & Dissocia<on

Dissocia<ve Sub<tu<on Mechanism

Dissocia<ve Sub<tu<on Mechanism

Commonly observed mechanis<c steps in organometallic chemistry include:

Oxida<ve Addi<on Reduc<ve Elimina<on Transmetalla<on Ligand Subs<tu<on Coordina<on Inser<on β-Hydride Elimina<on

An Example of an Oxida<ve Addi<on with a Non-transi<on Metal is the Grignard Reac<on (Magnesium is an alkaline earth metal).

Addi<on with a Non-transi<on Metal is the Grignard Reac<on (Magnesium is an alkaline earth metal).
Addi<on with a Non-transi<on Metal is the Grignard Reac<on (Magnesium is an alkaline earth metal).
Addi<on with a Non-transi<on Metal is the Grignard Reac<on (Magnesium is an alkaline earth metal).

Oxida<ve addi<on of Pd

1) Oxida<ve Addi<on of Pd to C-X

addi<on of Pd 1) Oxida<ve Addi<on of Pd to C-X Notes: a)   The oxida<ve addi<on

Notes:

a) The oxida<ve addi<on step increases the oxida<on state of the metal by 2. b) Therefore, it occurs most readily with electron rich metals and when the metal is in a rela<vely low oxida<on state (e.g. Pd(0)). It cannot occur when the metal is already at its highest oxida<on level. c) The reac<on proceeds most readily when the carbon is sp 2 hybridized (i.e. an aryl halide, or a vinyl halide).

Commonly used sources of Pd 0 include:

Commonly used sources of Pd 0 include: Tetrakis(triphenylphosphine)palladium (0) Pd(PPh 3 ) 4

Tetrakis(triphenylphosphine)palladium

(0)

Pd(PPh 3 ) 4

Tetrakis(triphenylphosphine)palladium (0) Pd(PPh 3 ) 4 Tris(dibenzylideneacetone)dipalladium (0) Pd 2 (dba) 3

Tris(dibenzylideneacetone)dipalladium (0) Pd 2 (dba) 3

Also, Pd(II ) is very readily reduced to Pd(0):

Also, Pd( II ) is very readily reduced to Pd(0): Thus, it is o`en more convenient

Thus, it is o`en more convenient to use Pd (II) complexes, which are more air-stable than commercial Pd (0) complexes.

2) Reduc<ve Elimina<on

2) Reduc<ve Elimina<on Notes: a)   This reac<on is the reverse of oxida<ve addi<on b)  

Notes:

a) This reac<on is the reverse of oxida<ve addi<on b) Therefore, the formal oxida<on state of the metal decreases by 2.

Relative rates of reductive elimination

L

L

CH 3 CH 3

CH 3

Pd

Pd CH 3

CH 3 3

+

solv

of reductive elimination L L CH 3 Pd CH 3 + solv -L L solv Pd

-L

L solv
L
solv

Pd

CH 3 RE CH 3
CH 3
RE
CH 3

LPd(solv)

+ CH 3

CH 3

Complex

Rate Constant (s -1 )

T( o C)

Ph 3 P

Ph 3 P Pd CH 3

Pd

CH 3 CH 3

1.04

x 10 -3

60

Ph 3 P

Ph 3 P CH 3

CH 3 3

 

MePh 2 P

MePh 2 P Pd

Pd

CH 3 CH 3

9.62 x 10 -5

60

MePh 2 P

MePh 2 P

CH 3 3

Ph

Ph

Ph Ph Ph P P Ph Pd CH 3 CH 3

Ph

P

P

Ph

Pd

CH 3 CH 3

CH 3 3

 

4.78

x 10 -7

80

 

Most crowded is the fastest reaction

Transmetalla<on

Transmetalla<on
Transmetalla<on

Now we will put the three reac<ons together (oxida<ve addi<on, transmetalla<on , and reduc<ve elimina<on) to produce some very widely u<lized processes which employ palladium (as Pd (0)) as a catalyst.

SUZUKI-MIYAURA CROSS COUPLING REACTION

SUZUKI-MIYAURA CROSS COUPLING REACTION
SUZUKI-MIYAURA CROSS COUPLING REACTION
Bagaimana Mekanismenya ??

Bagaimana Mekanismenya??

MECHANISM OF SUZUKI-MIYAURA CROSS COUPLING REACTION

MECHANISM OF SUZUKI-MIYAURA CROSS COUPLING REACTION

Selected examples of the Suzuki-Miyaura coupling in organic synthesis

Selected examples of the Suzuki-Miyaura coupling in organic synthesis

NOTED

When a reac<on is catalyzed by Pd (0), the mechanism for how it is produced from a Pd (II) precursor is o`en not discussed, and in some cases may not even be known. In the Suzuki reac<on, one way that Pd (0) can be generated is by homocoupling the boronic acid precursor:

is by homocoupling the boronic acid precursor: Because only a <ny amount of Pd (0) is

Because only a <ny amount of Pd (0) is required to catalyze the reac<on, a negligible amount of boronic acid is wasted, and only minor amounts of the homocoupling product are formed.

Negishi Cross-Coupling Reac<on

Negishi Cross-Coupling Reac<on
I
I

L = (PPh 3 ) 2

OR +

I L = (PPh 3 ) 2 OR + [Pd(PPh 3 ) 2 Cl 2 ]
[Pd(PPh 3 ) 2 Cl 2 ] ZnCl OR THF, 60 o C
[Pd(PPh 3 ) 2 Cl 2 ]
ZnCl
OR
THF, 60 o C

Predict the main products, include the mechanism

Predict the main products, include the mechanism

To understand the Heck Reac<on, two new processes will be introduced :

The inser<on reac<on The β-hydride elimina<on

Inser<on β-hydride elimina<on
Inser<on
β-hydride elimina<on

The inser<on reac<on

Inser<on
Inser<on
The inser<on reac<on Inser<on
The inser<on reac<on Inser<on

The β-hydride Elimina<on

β-hydride elimina<on
β-hydride elimina<on
The β -hydride Elimina<on β-hydride elimina<on

Heck Reac<on

Heck Reac<on
I Pd-Cat + n-Bu 3 N, DMF
I
I
I Pd-Cat + n-Bu 3 N, DMF

Pd-Cat

I Pd-Cat + n-Bu 3 N, DMF

+

n-Bu 3 N, DMF

I Pd-Cat + n-Bu 3 N, DMF

O

O

Br +
Br
+

O

O O Br + O O Pd-Cat THF, 60 o C

O

Pd-Cat THF, 60 o C
Pd-Cat
THF, 60 o C
O O Br + O O Pd-Cat THF, 60 o C

The Heck reac<on is named a`er Professor Emeritus Richard Heck of the University of Delaware. It is some<mes referred to as the Mizoroki -Heck reac<on, to recognize the early contribu<ons of the late Tsutomu Mizoroki , a professor at the Tokyo Ins<tute of Technology . In recogni<on of Prof. Heck’s contribu<on to the field of organopalladium chemistry, he was awarded the Nobel prize in Chemistry in 2010, along with Akira Suzuki (Hokkaido University) and Ei-ichi Negishi (Purdue University) for their eponymous palladium-catalyzed cross coupling reac<ons.

and Ei-ichi Negishi (Purdue University) for their eponymous palladium-catalyzed cross coupling reac<ons.