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Inorganic Chemistry (ll).

Course Outline
Academic Year 2017/18

Chapter 1. An Introduction to Coordination Chemistry. Coordination compounds.


Representative ligands. Coordination numbers and geometry. Molecular Orbital
Theory of Coordination Compounds. The eighteen-electron rule.

Chapter 2. Electronic spectra of complexes. Selection rules. Spectroscopic


terms. Terms of the free ion. Oh and Td complexes: the Weak Field Approximation.

Chapter 3. Magnetic properties of transition metal complexes. Magnetic


Susceptibility. Orbital and spin contributions to the magnetic moment. Ferro-, ferri,-
and antiferro-magnetism.

Chapter 4. An introduction to Organometallic Chemistry. Representative


organometallic ligands: carbon monoxide, organic C-donor ligands, phosphines,
hydride and dihydrogen ligands. Compounds with metal-metal bonds. Metal
clusters.

Chapter 5. Kinetics of ligand substitution reactions. Labile and inert complexes.


Classification of ligand substitution mechanisms. Ligand substitution in square
planar complexes. Trans effect and trans influence.

Chapter 6. Elementary reactions in organometallic Chemistry. Homogeneous


catalysis. Catalytic cycles.
Chapter 7. The structure of solids. Unit cells and crystal systems. Bravais lattices.
Symmetry operations and symmetry elements. Space groups. Closed packed
structures. Coordination polyhedra. Some important structure types. Defects and
non-stoichiometry.

Chapter 8. The bonding in solids. Band Theory: the linear chain of hydrogen
atoms. Bloch functions. Peierls distortion. Bonds in two and three dimensions. The
electronic structures of solids.

Chapter 9. Extended solids of p-block elements. Extended silicon-oxygen


compounds. Zeolites.

Chapter 10. lonic solids of s, d and f-block elements. Representative examples of


oxides and chalcogenides. Spinels, perovskites and ilmenites.

Chapter 11. Reactions at solid surfaces. Introduction to heterogeneous catalysis.

Chapter 12. Synthesis of solids. The ceramic method: solid state reactions at high
temperatures. Sol-gel methods. Other synthetic procedures.
Seminar Contents:

- Electronic Spectra of coordination compounds


- Magnetic properties of complex ions. Kinetic of substitution reactions
- Organometallic chemistry I
- Organometallic chemistry II. Metal clusters
- Structure of solids
- Band Theory
- Properties of solids of s, p d and f block elements.

Profesores encargados de la asignatura (teoría y seminarios):

Ernesto Carmona Guzmán guzman@us.es


M. Carmen Nicasio Jaramillo mnicasio@us.es
Jesús Campos Manzano jcampos2@us.es
Bibliography

- Organometallics and Catalysis. An Introduction, M. Bochmann. Oxford


University
Press, 2015.

- Inorganic Chemistry, C. E. Housecroft, A. G. Sharpe, 3rd 'Ed., Pearson,


Prentice Hall, 2008.

- Inorganic Chemistry, P. W. Atkins, T. Overton, J. Rourke, M. Weller, F.


Armstrong, 4th
Ed. McGraw-Hill, 2008.

- The Organometallic Chemistry of the Transition Metals, R. Crabtree, 5a Ed.,


John Wiley and Sons: 2009.

- Inorganic Structural Chemistry, U. Müller, 2a Ed., Willey: 2007.

- Basic solid state chemistry, A. R. West, 2a Ed. John Wiley and Sons: 2014.

- Solid State chemistry: an introduction, E. Lesley, E. Smart, A. Moore, 3a d,


Chapman and Hall, 2005.
Chapter 1.

Coordination compounds. Representative ligands. Coordination numbers and


geometry. Molecular Orbital Theory of Coordination compounds. The 18-electron
rule.
The Nobel Prize in Chemistry 1913 was awarded to Alfred Werner
"in recognition of his work on the linkage of atoms in molecules by
which he has thrown new light on earlier investigations and opened
up new fields of research especially in inorganic chemistry".
Alfred Werner, Chemistry Nobel Prize, 1913

2+ 2+
N N
N Cl Cl N
Co Co
N NH3 H3N N
N N

N-N = H2NCH2CH2NH2

6+
[Co]
H HO
O OH
[Co] Co [Co] = Co(NH3)4
O O
H HO H
[Co]
Remove Cp
Ligands: neutral or charged atoms or molecules that posses one or more donor atoms (i.e. atoms that can
share electron density from a lone pair). General symbol: L

Neutral L do not contribute to the M oxidation state. They behave as 2e- donors. For instance:
:NH3 (2e-); en = H2NCH2CH2NH2 (2x2=4e-). In general L or L L, etc.

Anionic L contribute with 1- (in general n-) to the M oxidation state. In the covalent formalism they are
viewed as radicals and act as 1e- donors. General representation: X

F : -1 charge.; F 1e- donor

2-
O charge -2; O 2e- donor

etc.

a ligand like
H H
H3C C CH3 H3C C CH3

C C C C

O O O O

bidentate, monoanionic ligand; charge -1; 3e donor (XL)


Halide ligands may act as terminal or as bridging ligands (charge -1)

Cl Cl
M Cl
M M M M
- - -
1e 3e 5e M

NO terminal nitrosyl (π-acceptor): formally NO+, 3e- donor: M N O lineal


bent nitrosyl, NO-, 1e- donor: M N
O

chelating ligands

they occupy two or more metal coordination sites

H2NCH2CH2NH2 = en, bidentate; acac, carboxylates, etc.

bipy, o-phen, and many others

B
Tp': tridentate
N
N
N
N
N
N
Crown ethers; cryptands,...: multidentate ligands

π-DONOR LIGANDS: they possess lone pairs of e- in orbitals of π symmetry:

π
M L
σ

Generally anionic like F-, O2-, R2N-, RN2-, etc.

π
F as radical F σ M equiv. to F M

3e-

O O M, but also: O M

2e- 4e-

R O M O 1e-
R
M O 3e- equiv. to M O
R R
M O R 5e-, M O R
lineal

2-
Similar comments for R2N y R N
π
π-ACCEPTOR LIGANDS. They posses empty, low-lying orbitals of π symmetry: M L π back-donation
σ
Some Examples: CO, NO, PR3, C C , C C
Also H2, O2, N2,..........

CO, NO, alkenes, alkynes: π* m.o.

H2 : σ* m.o.
O2, N2 : also π* m.o.
etc, etc.

Organic ligands with C-donor atoms

Alkyl, aryl and related groups. Formally monoanionic, e.g. CH3-, C6H5-, .... They are viewed as radicals, hence 1e- donors

alkenes and alkynes:


C C C C

M M
2e-; η2 2e-; η2

σ-component of the bond: L (π) M(dσ)


Allyl groups: three carbon donor atoms, H2C CH CH2

formally alkyl plus alkene,

Accordingly, monoanionic, bidentate, 3e- donors.

but also: M CH2

monodentate η1 - C3H5, 1e- donor


[M]
(η3 - C3H5)

- Diene ligands (4C) Bidentate (2 coordination sites)

Neutral, 4e- ligands

[M]
η4 - C4H6

Ciclopentadienyl (5C)

3 coordination positions (for instance, [M]


CpML3; Cp, a face of the Oh) η5 - C5H5, formally Cp-, 5e- donor
It can also coordinate as η 3-Cp (3e-) or η1-Cp (1e-)

** C 5Me5 Cp* (L 2X)

ARENES
three coordination sites (L3); 6e- donor ligands

(η 6-C6H 6)

Cr
Cr(C6H6)2

Electron - counting Rules

CrCl3(NH 3)3 :

A) covalent formalism: 6(Cr)+3(Cl)+3x2(NH3 )=15e-

B) ionic formalism: Cl-, 2e -; but M n+ with corresponding e-

3(Cr3+)+6(Cl-)+6(NH3)=15e-
7(Mn)+(CH3)+5 x 2(CO)=18e- 7(Mn)+(CH3)+5 x 2(CO)=18e-
+1 (-1) (+2) (-1) (-1)
Mn(CH3)(CO)5 Ni(C6H5)Cl(PMe3)2

6(Mn+)+2(CH3-)+5 x 2(CO)=18e- 6(Mn+)+2(CH3-)+5 x 2(CO)=18e-

+1 (-1)
Mn(η -C3H5)(CO)4: Mn(I), d7, 6-coordinate.
3
EAN= 7(Mn)+3(al.)+8(4CO)=18e-

(-1) (+2) 2x(-1) +1


5
(η -C5H5)Mo(CH2CMe3)2(NO)(PMe3) Mo(II): d6; 7-coordinate EAN=5+6+2+3+2=18e-

(OC)5 Mn Mn(CO)5 Mn(0), d7 EAN=7+1(Mn - Mn)+10(CO)=18e-

O
C H

(η5-C5H5) Rh Rh (η5-C5H5) H C C
H
C
O
4(C)+3(H)+1(C-C)

5+9+2x1+2(Rh = Rh) =18e-


Coordination Compounds

Molecular Orbital Theory.


The Eighteen-electron Rule (or Effective Atomic
Number Rule)
5. Componente Angular.
Estructura
Forma angular de los orbitales atómicos atómica

Función Angular, Yl,ml (θθ,φφ)


Orbitales d

Planos NODALES = 2
Radial extension of atomic orbitals nd, (n+1)s y (n+1)p

Orbital size increases upon


decreasing the M formal
oxidation state.
Also:
3d < 4d < 5d
i
Oh E 8C3 6C2 6C4 6S4 8S6 3σh 6σd

A1g 1 1 1 1 1 1 1 1 1 1 X2 + y2 + z2

A2g 1 1 -1 -1 1 1 -1 1 1 -1

Eg 2 -1 0 0 2 2 0 -1 2 0 (2z2 – x2 – y2, x2 – y2)

T1g 3 0 -1 1 -1 3 1 0 -1 -1 (RX, RY, RZ)


T2g 3 0 1 -1 -1 3 -1 0 -1 1 (xz, yz, xy)

A1u 1 1 1 1 1 -1 -1 -1 -1 -1

A2u 1 1 -1 -1 1 -1 1 -1 -1 1

Eu 2 -1 0 0 2 -2 0 1 -2 0
T1u 3 0 -1 1 -1 -3 -1 0 1 1 (x, y, z)
T2u 3 0 1 -1 -1 -3 1 0 1 -1
ML6(σ) ML6(σ + π) 6L(π-donors)

eg* eg*

∆0
∆0 t2g

t2g

t2g
t2g

σ bond π bond π-donor ligands


ML6(σ) ML6(σ + π) 6L(π-acceptors)
t2g

eg* eg*
t2g
∆0

t2g ∆0

t2g

σ bond π acid bond


Factors that determine the
Coordination
value of 10Dq
Compounds
↑↑ 10Dq ⇒ Strong-field Complexes
↓↓ 10Dq ⇒ Weak-field Complexes

1.- Geometry of the complex 10DqOh ~- (4/9) · 10DqTd

2.- Metal oxidation state M An increase in oxidation state increases 10DqOh

3.- Nature of M 1st T.S. < 2nd T.S. < 3rd T.S.

SPECTROCHEMICAL SERIES
4.- Nature of the ligands

I- < Br- < S2- < SCN- < Cl- < NO3- < N3- < F- < OH- < O2- <... Weak-Field Ligands

...< H2O < NCS- < CH3CN < py < NH3 < en <... Intermediate-Field Ligands

...< CH3 < H- ~ CN- < PR3 < NO < CO Strong-Field Ligands
The 18-e- rule (EAN rule)
n(d) n(VE)
0 12
1 13

t1u* 2 14
3 15
4 16
5 17

a1g* 6 18
np 7 19
8 20
9 21
10 22
ns eg*

(n-1)d ∆0 t
2g
σ
M L
Class I

a1g, eg, t1u EAN > 18 or < 18


The 18-e- rule (EAN rule)
n(d) n(VE)
0 12
0 12
t1u* 1 13
2 14
3 15
4 16

a1g* 1 17
np 2 18
4 16
5 17
6 18

ns eg* 8 16

(n-1)d ∆0 t
2g
σ
M L
Class II

a1g, eg, t1u EAN < 18


n(d) n(L) n(VE)
6 12 18
7 11 18
6 12 18
8 10 18
10 8 18
9 9 18
10 8 18
8 10 18
6 12 18

Cr(CO)6

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