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CHEM3341

Inorganic
Chemistry II
(4 Year
Dr. Angela Yuen
E-mail: maiyan@hku.hk Curriculum)
Office: Rm 407, Hui Oi Chow Science Building

1
CHEM3341
 Lectures
- Dr. Angela Yuen (15 lectures)
4Sep to 21Sep; 6Nov to 30 Nov;
+ 1 Make-up lecture due to public holiday
- Prof.Vivian Yam (9 lectures)
25 Sep to 2 Nov + 1 Make-up lecture due to public holiday
 Tutorials
 Continuous Assessment
- Practical (~15%)
- Assignments (~10%)
 Written Examination (3 hours, ~75%)

2
Lab Arrangement
 Class A: Monday Morning 9:30-1:30 pm
 Class B: Thursday Morning 9:30-1:30 pm

 Please be punctual!
 Submit your lab report within one week
after you finish your experiment.
Tutorial Schedule
 Make-up lecture 3 Oct 2017 Tue 6:30-
7:30pm
 Dr. Yuen’s Tutorial
 Mon 4:30-5:30 pm or Tue 6:30-7:30 pm (Two
tutorial classes offered the same content)
◦ Tutorial 1: 11 Sep &12 Sep
◦ Tutorial 2: 25 Sep & 26 Sep
◦ Tutorial 3: 20 Nov & 21 Nov
◦ Tutorial 4: 27 Nov & 28 Nov

 Tutor: Miss Jenny Yeung


jennyyyw@connect.hku.hk
Tutorial Schedule (Prof.Yam’s Part)
Contents:

1) Organometallic Chemistry
2) Important inorganic molecules/
reactions in biological systems
3) Characterization of Inorganic
Complexes
4) Inorganic Reaction Mechanisms
5) Kinetic studies of inorganic reactions

6
Review: Coordination Compound

trans-[Co(en)2Cl2]+

cis-[Co(en)2Cl2]+
What is organometallic chemistry ?
 Strictly
speaking, the chemistry of
compounds containing at least one metal-
carbon bond.
 Metal hydrides are often included, H being
considered as the "smallest organic group”

(AlMe3)2 Al Al

8
What is organometallic chemistry ?
 Metal-carbon bonds are often formed temporarily or potentially,
so in practice many compounds are included that do not actually
contain metal-carbon bonds.
PPh3
H Rh H
oxidative
addition Cl coordination
H H PPh3
R

PPh3
-PPh3 Cl
[RhCl(PPh3)2] RhCl(PPh3)3
+PPh3 H Rh H
Wilkinson’s
R PPh3
Catalyst

reductive
elimination PPh3 migratory
Cl Rh H insertion
R
PPh3
H H
H
R
References
1) R.H. Crabtree, “The Organometallic Chemistry of
the Transition Metals”, Wiley ( New York), the 2nd
Edition (1994).
2) J.E. Huheey, E.A. Keiter and R.L. Keiter, “Inorganic
Chemistry” 4th Ed. (1993). Harper Collins ( New
York).
3) D.F. Shriver, P.W. Atkins and C.H. Langford,
“Inorganic Chemistry”, 3rd Ed., 1999 (OUP).
4) E.A.V. Ebsworth, D.W.H. Rankin and S. Cradock,
“Structural Methods in Inorganic Chemistry” 2nd
Ed. Blackwell Scientific Publication (Oxford), 1991.
5) F.A. Cotton, G. Wilkinson, C.A. Murillo and M.
Bochmann “Advanced Inorganic Chemistry”, 6th
Ed. Wiley, (New York), Latest Edition
10
Why studying organometallic
chemistry?
 Organometallic chemistry is the basis of homogeneous
catalysis, which is the method of choice for clean and
efficient synthesis of fine chemicals, pharmaceuticals and
many larger-scale chemicals.
 Many plastics(polythene, polypropene, butadiene rubber, ...)
and detergentsare made via organometallic catalysis.
 Organometallic chemistry is also the basis for understanding
important steps in heterogeneous catalysis reactions such
as olefin hydrogenation and CO oxidation.
 Organometallic compounds are used on a large scale as
precursors for generation of semiconductors (AlN, GaAs,
etc).
 Silicone rubbers are one of the few classes of
organometallic compounds used as "final products".
1. Examples of Organometallic
Compounds

.
1. K[Pt(C2H4)Cl3] H2O

Zeise’s salt in 1827


1st transition metal organometallic compound

12
2) Grignard Reagent
 One of the most valuable synthetic
tools in the organic chemistry The Nobel Prize
in Chemistry
1912

RMgX R=alkyl, arene


X=Cl, Br, I
In solution (e.g. ether) L L
X

Mg Mg
2RMgX
R X R
Schlenk equilibrium L = solvent
R X L
R2Mg + MgX2
Mg Mg
13
R X L
3) Ni(CO)4 Mond (1890)
Prepared by: 1atm
Ni(metal) + CO(g) Ni(CO)4
°C
Colourless
excess
volatile liquid
m.p. -19.3 °C
b.p. 42.2 °C
Structure of Ni(CO)4:
 Tetrahedral both in gas and solid
OC CO
phase
Ni  Ni–C 1.84Å
 C−O 1.1Å
OC CO
 Very toxic molecules
14
Ni(CO)4  Ni + 4CO
Thermal
decomposition

Important Industrial Application:


Purification of Nickel metal
(The Mond process)

15
The Mond Process
Nickel Ni Crude + CO 1atm Ni(CO)4
Oxide H2 mixture excess 500C

recycle 230oC

4CO + Ni
99.95%
C + H2O H2 + CO
 Water-gas shift Reaction
 provides H2 and CO 16
4) Ferrocene / Metallocene
 Fe(C5H5)2 1951
 Structure:
Sandwich compound

G.Wilkinson E.O. Fischer


Fe
The Nobel Prize in Chemistry 1973

 Found to be general for metal ions

M Metallocene: M(ɳ5-C5H5)2
17
5) Vitamin B12-coenzyme

D.C. Hodgkin
The Nobel Prize
in Chemistry 1964
For The X-ray
analysis of
Complicated
Co(III) Molecules

http://en.wikipedia.org/wiki/Vitamin_B12 18
 Important catalyst in biochemical systems
 Catalyze 1,2-shifts

R=H R H R
or CH3
C C C C

H H H

 The reactive Co–C bond


participates in 1,2 shifts
 Methyl transfer
Important for carbon skeleton
re-arrangement 19
A large variety of Metal Carbon
bonding interaction has been
observed.
M-C single bond
(usually regard as
as in Grignard Reagent 2 centre-2 electron covalent bond)

Metal –  complexes

Ferrocene type Zeise’s salt


20
Metal-Carbon Multiple bonds

metal carbene metal carbyne


Double bond: 1 σ + 1 π Triple bond: 1 σ + 2 π

21
Example: Metal Carbene
(1
2.026Å

NaOMe
-MeOH 2.246Å
2.10Å
from the center
= Cp of the ring

 - deprotonation of an M-alkyl group


22
Example: Metal Carbyne
CH3

H3C CH3

Cl
H3C CH3 1.85Å(1+2)
Ta

Me3P C
Ph
PMe3

CH3

H3C CH3

= Cp*

H3C CH3 23
- Other metal carbon bond not possible to
assign a formal bond order
e.g. metal-carbido compounds

Interstitial atom
Ru Co
Fe Co

Ru
Ru
Fe C Co
Ru
C
Ru
Fe C Fe Co
Co
Fe
Ru
Co

[Fe5C(CO)15] [Ru6C(CO)17] [Co6C(CO)15]2-


24
Organic Ligands commonly found in
Organometallic compounds

CO carbonyl
Cyclobutadiene
(cyclo-C4H4)
Carbene
(alkylidene)
Cyclopentadienyl
Carbyne (cyclo-C5H5)(Cp)
(alkylidyne)

Cyclopropenyl
Benzene
(cyclo-C3H3)
25
Organic Ligands commonly found in
Organometallic compounds
1,5-cyclooctadiene
(1,5-COD) -Allyl (C3H5)
(1,3-cyclooctadiene
complexes
are also known)
Alkyl
CH2 CH2 Ethylene

Acetylene Acyl

26
Nomenclature for Organic Ligands

n - describe the no. of metal atom bridging


by the ligand
n=2, 3, 4, .…

x - describe the no. of atom in the ligand


involve in bridging of the metal centres

27
Examples:
CO CO

Mo
Mo Mo Mo Mo

2-CO 3-CO

CH2

LnM
Mo
CH2
CO CO CO

2-C2H4 6-C6H6 28
How do you describe the organic
ligands in the following
compounds?
Electron
Counting for
Organometallic
Compounds
18 Electron Rule
18-electron rule
 Many stable organometallic compounds
have 18 electrons in the metal valence
shell.
 i.e. sum of valence electron in the metal
ion and the electrons donated by the
ligands =18
CO
CO CO
Mo 6
 e.g. Mo(CO)6 6(CO) 12 Mo
CO CO
18
CO
31
Electron counting schemes of common Ligands
Closed Shell Neutral Ligand
Ligand Formulism Formulism

4 (C3H5-)
Electron counting schemes of common Ligands
Closed Shell Neutral Ligand
Ligand Formulism Formulism
(For Neutral Electron Count)
DO NOT mix up hapticity with the number of
electrons given by the ligand to the metal! 35
Example:
d electron count of Fe(II)
[Fe(C5H5)2]
Fe
Oxidation State
C5H5=

Covalent Model Ionic Model


Fe 8 Fe(II) 6
2(C5H5) 10 or 2 (C5H5-) 12
18 18

Group number of Fe

Electron count of neutral ligand


36
Example:

Covalent Model Ionic Model

37
Examples:
Ionic Model Covalent Model

aTo account for the positive ionic charge on the complex as a whole; for
anions, the net charge is added to the total. 38
Example:

Covalent Model Ionic Model

39
Example
For each Re
Re2(CO)10
CO CO Re 7
CO CO

OC Re Re CO
5(CO) 10
OC OC
M–M 1
CO CO 18

A M-M single bond contribute


1e for each metal

40
Question: For the following molecules,
give the valence electron count and the
oxidation state of the metal.

41
 Not all metal complex(include co-
ordination compounds/ organometallic
compounds) obey the 18e rule.

e.g. [TiF6]2− 12e


[Cu(NH3)6]2+ 21e
PtF6 16e
V(CO)6 17e
W(Me)6 12e

42
21 22 23 24 25 26 27 28 29

Sc Ti V Cr Mn Fe Co Ni Cu
Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper

39 40 41 42 43 44 45 46 47

Y Zr Nb Mo Tc Ru Rh Pd Ag
Yttrium Zirconium Niobium Molybdenum Technetium Ruthenum Rhodium Palladium Silver

57 72 73 74 75 76 77 78 79

La Hf Ta W Re Os Ir Pt Au
Lanthanum Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold

Early Transition Middle Transition Late Transition


Metals Metals Metals
16e and sub-16e 18e 16e and sub-16e
configurations configurations configurations
are common are common are common
Coordination Coordination Coordination
geometries geometries geometries
higher than 6 of 6 are common of 5 or lower
Because

(a) These compounds usually with metal in


relatively high oxidation states
i.e. relatively few electrons ( Mn+)
to achieve 18e configuration
 more ligand is required.
But inter-ligand repulsion usually prevent
this.
e.g. [TiF6]2-  12e (Steric crowding)
if 18e  [TiF12]2- ==>unfavorable
44
(b) the usual type of ligands such as Cl-, H2O,
NH3 are weak field ligands
(i.e. low in the spectrochemical series)

Consider the molecular orbital diagram for


an octahedral complex.

45
Size of Δ depends on the
nature of the ligands:

•Weak field ligands 


small Δo
•strong field ligands 
large Δo

46
For metal complexes with σ-donar ligands:
o is relatively small

t2g set of orbitals is non-bonding can be


occupied by 0-6e.
eg* set of orbitals is weakly-antibonding can
take 0-4e.

Then bonding orbitals 12e


+
non-bonding and 0 10e
weakly antibonding
12 22e 47
- Note that many d8 metal complexes in group
9 and 10 [e.g. Rh(I), Ir(I), Pd(II), Pt(II)] favour
a square planar geometry and obey 16 electron
rule.

Consider the MO diagram of square planar


complexes

48
dx2-y2
* the relative positions
of 
dz2 and dxy can be
changed depending on dz2
different molecules dxy

dxz , dyz

bonding
orbitals

 is large in these compounds and dx2-y2 is not


populated.
49
CO as a
ligand

Metal Carbonyl Complexes

50
Bonding Properties of CO
• -donor and -acceptor ligands

• Have a -donor orbital containing an electron pair and


also have vacant orbitals of  symmetry which are at an
energy suitable for accepting electron density from
occupied metal d orbitals.

• 2-electron donor ligand


i.e., the lone pair on the C atom is used to
form a bond to the metal.

• It forms compounds with most of the transition metals


in their low or zero (even negative) oxidation states. 51
MO diagram of CO

- a triple bond between C and O

- the Highest Occupied Molecular Orbital (HOMO) is weighted towards


carbon.

- the Lowest Unoccupied Molecular Orbital (LUMO) is also weighted


towards carbon. 52
Binding Modes
Terminal CO

-donor interaction,
bonding
When CO acts as a ligand,  orbital serves as a donor
to the metal centre and forms a  bond.

53
-acceptor interaction,
back-bonding
* orbitals (LUMO) of CO at the same time can
overlap with metal d-orbitals that have local 
symmetry (i.e. t2g set in octahedral field).
 back-bonding
54
M() <── CO ()
-donor interaction,
bonding

very minor
contribution
-can be neglected

55
- This type of bonding between metal and ligand is said to be synergistic
because two types of interaction are mutually re-enforcing.

(a) -donation to the metal center increases the electron density at the
metal center, hence increase the delocalisation into the CO *
orbitals.

(b) The electron density from the metal centre delocalised to CO *


results in an increase in the effective nuclear charge of the metal, therefore
a stronger ligand to metal  bond can be formed.

56
Evidences for back bonding
- Bond distances (X-Ray)
- CO stretching frequency (IR)
e.g.
CH2
Fe-CO 1.75(2)Å
CH2
Fe-C(sp3) 2.20(2)Å
CH2
CO
OC Fe
CO
CO

Covalent radii of C (sp3) = 0.77Å


Covalent radii of C (sp) = 0.64Å
Difference = 0.13Å
57
  Fe-C(sp)  2.07Å (pure Fe-C single
bond)
CH2

CH2 But now Fe-CO = 1.75Å


Multiple bond nature of Fe-CO
CH2
CO
OC Fe  C-O bond lengths for metal carbonyl
CO
CO are slightly longer than that of the free
CO ( typically 1.15Å vs 1.128Å).
 But the difference is usually too small
to draw a firm conclusion.

58
- The C-O force constant (Stretching frequency)
is much more sensitive measure of changes in
bond order.

When the back-bonding occur, the CO bond


order should be reduced (electron goes to *
orbitals).

e.g. free CO 2143cm-1


Cr(CO)6 2000cm-1

59
Synthesis of Metal Carbonyl
complexes
(1) Direct reaction of metal
 involved reaction of a metal powder with
excess carbon monoxide gas under
appropriate conditions

300C, 1 atm
e.g. Ni(s) + CO(g) Ni(CO)4 >90%

2000C, 15h, 200atm


Fe(s) + CO(g) Fe(CO)5 26%

1500C, 35 atm
Co(s) + CO(g) Co2(CO)8 90%

2000C, 250 atm


Mo(s) + CO(g) Mo(CO)6 30% 60
(2) Reductive Carbonylation

- direct reaction is impractical for many other d-block metals.

- reductive carbonylation involves the reduction of a salt or


metal complexes in the presence of CO

-reducing agents commonly used are: Al metal, Na metal, Al


alkyl compounds, H2 gas or CO gas itself.
e.g.
AlCl3 cata
CrCl3 + Al(s) + CO(g) C6H6 Cr(CO)6 + AlCl3 88%

WCl6 + 3Et3Al + CO(g) C6H6


W(CO)6 92%

250oC, 350atm, 16 h
Re2O7 + 17CO(g) Re2(CO)10+7CO2 95%
61
(2) Reductive Carbonylation
MeOH
Ru(acac)3 + H2(g) Ru3(CO)12 + CO(g)
150oC
82%

o o
acac =

62
(3) From other metal carbonyls
Thermal or photochemical reaction of other binary
carbonyls
h 95oC
e.g. Fe(CO)5 Fe2(CO)9 (90%) Fe3(CO)12 (10%)

Os5(CO)16
Os3(CO)12 Os6(CO)18
 Os7(CO)21
Os8(CO)23
Os5C(CO)15
Os8C(CO)22
[Os10C(CO)24]2−

Co2(CO)8 Co4(CO)12 (100%)


63
Some Reactions of Metal Carbonyl
 Ligand Substitution

L : Phosphines,
CH3CN or
other ligands

 Migratory insertion: Involves the reaction of CO with


an alkyl complex to give an acyl product
CH3 H3C H3C CO
OC CO C CO CO C CO
Mn O Mn O Mn
OC CO OC CO OC CO
CO CO CO
64
Structure of Metal Carbonyl
Complexes
Compound M−C distances (Å)
Ni(CO)4 1.838

Fe(CO)5 (a) (b)


Fe-C (axial) 1.810 1.814
Co
Fe-C (eq.) 1.833 1.812
CO
OC Fe (a): electron diffraction
CO (b): x-ray at -120oC
Co
Cr(CO)6 1.913(2)
Mo(CO)6 2.06(2)
W(CO)6 2.06(2)

65
C–O Stretching frequency
•CO depends on both the no. of metal it bridges and
the charge on the metal complexes
•More metal atoms the CO ligand interacts with, the
larger the electron back donated to *.

Free CO 2143cm−1

Metal
Carbonyl CO 1850-2120cm−1
[Mn(CO)6]+ 2090cm−1
[Ni(CO)4] 2060cm−1 1750-1850cm−1
[Cr(CO)6] 2000cm−1
[Co(CO)4]− 1890cm−1 1620-1740cm−1
[V(CO)6]− 1860cm−1
[Fe(CO)4]2− 1790cm−1

66
IR stretching
freq of free CO
is 2143 cm–1

IR stretching frequency of CO is lowered upon metal coordination


This is due to changes in energy between d and * of CO
orbitals and the amount of electron density back donated to
CO antibonding orbitals changes.

Higher negative
charge on the ==> d-p ==> CO
metal interaction
67
Example:

IR spectrum shows bands in


the bridging and terminal regions
The number of IR
active bands as
determined by group
theory
Questions
Given the following information, explain the
difference in (CO).
CO gas 2143cm−1
H3B.CO 2164cm−1
Mo(CO)6 2001cm−1

70
Structure of Metal Carbonyl Complexes
 The metal-carbonyl distances reflects the variation in
covalent radii of the metal atoms.
 C–O distance in metal complexes: 1.14-1.20Å usually
 M–C–O angle: 165o-180o
 Deviation from linearity may arise from inter-molecular
packing forces or from intra- molecular bonding interactions.
 The carbonyl ligand co-ordinates to metal atoms through the
carbon atom.
 Metal–metal bonds are involved in polynuclear metal
carbonyl usually.
Ir

Os
Ir
Re Re Os Os
Ir Ir

Re2(CO)10 Os3(CO)12 Ir4(CO)12 71


Example:

72
Bridging CO
Overlap of  and  orbitals of bridging carbonyl ligands with the d
orbitals of the metal atoms.

 The  orbital of CO can  the emply * orbital of CO


donate electron density to can accept electron density
the metal orbitals from metal d orbitals

Kostie, N.M; Fenske, R.F.; Inorg. Chem. 1983, 22, 666-671 73


Bridging carbonyl
O

Various coordination modes have been


C
observed.
M M

Structure Name Conditions


Symmetrical a=b
2-CO = 
  CO vector
 perpendicular to
MM

Asymmetrical ab
2-CO CO vector
perpendicular to
MM
74
Structure Name Conditions

semi-bridging ab
2-CO  

CO vector NOT
perpendicular to MM

Linear CO   180o

75
The bonding enthalpy for each M-C bond to 2-CO ligands is
approximately half the M-CO (terminal) bond enthalpy for a
given metal atom.

CO
C

 M M  M M

C
CO

very similar in energy

76
Terminal and Bridging CO
 Facile exchange between terminal and bridging CO
ligands is observed and can be detected by 13C NMR.

 Prediction of the terminal or bridging CO ligands in one


structure is not yet possible.
 However, heavy metal complexes such as Os3(CO)12,
Ru3(CO)12, Ir4(CO)12, tend to have an all terminal CO
structure.

77
- Bridging CO is a better  acceptor and tends
to appear in highly charged anionic compounds.

Approximate range for the CO stretching frequency in


neutral metal carbonyl.
Bonding Mode (CO)/cm−1
Terminal CO 1850-2120
2-CO 1750-1850
3-CO 1620-1730

78
Coordination Modes for CO in the Metal Cluster Complexes

79
Fischer-Tropsh Synthesis
 Conversion of mixtures of CO and
hydrogen into Hydrocarbons
 Heterogeneous catalysts needed: Fe, Ru
metals
 Mixture of products: both saturated and
unsaturated HCs

n CO + 2n H2 -(CH2)n- + n H2O

80
H2 +CO

O Absorption of CO + H2
H H C
Syngas molecules

H H C O
Dissociation of CO + H2

CH2 H H
CH3 CH O Hydrogenation of C and O
CH2 H H
CH3 CH Hydrogenation of
O
C and O

CH4
H2O
CHn H H Methanation
CH4 H O
CHm

Propagation
Monomer CH p chain
H
C 2H p
Initiation
Metal Carbonyl Clusters : Model
for Surface
(CO)3
Source of Carbide : CO ligands Fe

 (OC)3Fe Fe(CO)3
Fe3(CO)12
C
(OC)3Fe Fe(CO)3

Reactivity of a surface carbide *formation of a C-C bond

[ Fe4(CO)12C]2-

83
Other ligands…
 Other ligands (-donor / -acceptor) which bond to
metal in a qualitatively similar manner to CO.
 e.g. N2, CN−, NO+, CNR
 Their properties as ligands largely depend upon the
electronegativity difference between the ligand atoms
and the overall charge.

N2 - poor -donor, poor -acceptor


CN− - better -donor, poorer -acceptor Compared
NO+ - similar -donor, -accepter property with CO
CNR - slightly better -donor, slightly poorer
-acceptor
84
Phosphines
:PR3 - very important ligands
- -donors
- -acceptors
PR3 excellent ligands for soft late transition
metals

85
accepting ability
-back-donation occurs into MOs formed by combination of
two d-orbitals on phosphorus and the * orbitals involved in
P-R bonding.

P + P P

d-orbitals * orbitals acceptor MOs

P + P P

 acceptor

86
Steric properties:
 The size of ligands can be measured using
the concept of a cone angle (Chadwick A.
Tolman, Chem. Rev., 1977, 313).
 Tolman angle
 R1

M P R2

R3

T he cone angle
Apex angle of a cone that encompasses
the van der Waals radii of the outermost
atoms of the ligand 87
Electronic properties
 Electronic properties measured by IR – (CO)
measured for a large series of carbonyl
phosphine complexes with different PR3 (e.g.
[Ni(CO)3(PR3)] or [CpFeMe(CO)(PR3)])
 Stronger donor phosphines increases the
electron density of metal, thus increasing the
ability of p-back donation
 (CO) decreases
 PCy3 > PEt3 > PMe3 > PPh3 > P(OMe)3 >
P(OPh)3 > PCl3 > PF3

88
y-axis = (CO) for [Ni(CO)3L]

x-axis = cone angle ()


89