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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
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
12
2) Grignard Reagent
One of the most valuable synthetic
tools in the organic chemistry The Nobel Prize
in Chemistry
1912
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
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
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
Metal – complexes
21
Example: Metal Carbene
(1
2.026Å
NaOMe
-MeOH 2.246Å
2.10Å
from the center
= Cp of the ring
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
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
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=
Group number of Fe
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:
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
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.
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
45
Size of Δ depends on the
nature of the ligands:
46
For metal complexes with σ-donar ligands:
o is relatively small
48
dx2-y2
* the relative positions
of
dz2 and dxy can be
changed depending on dz2
different molecules dxy
dxz , dyz
bonding
orbitals
50
Bonding Properties of CO
• -donor and -acceptor ligands
-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.
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
58
- The C-O force constant (Stretching frequency)
is much more sensitive measure of changes in
bond order.
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%
1500C, 35 atm
Co(s) + CO(g) Co2(CO)8 90%
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−
63
Some Reactions of Metal Carbonyl
Ligand Substitution
L : Phosphines,
CH3CN or
other ligands
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
Higher negative
charge on the ==> d-p ==> CO
metal interaction
67
Example:
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
72
Bridging CO
Overlap of and orbitals of bridging carbonyl ligands with the d
orbitals of the metal atoms.
Asymmetrical ab
2-CO CO vector
perpendicular to
MM
74
Structure Name Conditions
semi-bridging ab
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
76
Terminal and Bridging CO
Facile exchange between terminal and bridging CO
ligands is observed and can be detected by 13C NMR.
77
- Bridging CO is a better acceptor and tends
to appear in highly charged anionic compounds.
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
[ 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.
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
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]