Organometallic Chemistry and Catalysis

Organometallic Chemistry and Catalysis

An area which bridges organic and inorganic chemistry
A branch of coordination chemistry where the complex
has one or more metal-carbon bonds
The metal-ligand interactions are mostly  acid type
M-C bond can be a  type or  type bond

C C
M  M *
C C

donation from  back donation to *

O O
CH3
R3P CO R2 C C R2 Ph3P PPh3
Re
P
Mo
Cl
Mo
P
Rh
PR3 P Cl P Ph3P
R2 C C R2 Cl
CO
O O
 What all compounds are considered as organometallic?

C always more electronegative compared to M

The leading journals of the field define an "organometallic" compound as one in which there is a bonding
interaction (ionic or covalent, localized or delocalized) between one or more carbon atoms of an organic
group or molecule and a main group, transition, lanthanide, or actinide metal atom (or atoms).
Following longstanding tradition, organic derivatives of the metalloids such as boron, silicon, germanium,
arsenic, and tellurium also are included in this definition.
It is also understood that the element to which carbon is bound is more electropositive than carbon in
organometallic chemistry.

Traditionally metal cyanide complexes are not considered as organometallic

 CO CO CO
Metal carbonyls CO OC CO
Ni OC Fe Cr
CO OC CO
OC CO
CO
CO CO

O
CO OC CO C CO
OC OC

OC Mn Mn CO Co Co CO
OC
OC CO OC CO
CO OC C
O

CO
OC
CO CO
OC CO Ir
OC
CO Os CO CO
OC
OC CO Ir Ir
OC CO
Os Os Ir CO
OC CO CO OC
OC CO
CO CO

Coordination number around the metal normally remains six or lesser.

17 electron species such as Mn(CO)5, Co(CO)4 dimerize to gain 18 electrons

V(CO)6 does not dimerize.

 Why study metal carbonyls ?

Simplest of organometallic compounds where M-C  bonding is well understood. CO is one of the strongest
 acceptor ligands. Back bonding ( bonding) and variation in electronic properties of CO can be monitored
very efficiently by Infrared spectroscopy

A range of metal carbonyls are used as catalysts in Chemical Industry

Hydroformylation
Methanol to Acetic acid Process
Alkene to Aldehyde

R
C CH2 MeOH + HI MeI + H2O
H
CO H3C C I
MeI
CO,
HCo(CO)4 H2 [Rh(CO)2I2] O
H2O
R H3C C I H3C C OH
CH CH2
O O
H HC
O
 *
Molecular Orbital diagram of CO
*
Why does CO bind a metal through its less electronegative LUMO
carbon atom than its more electronegative oxygen ? What
makes it a good  acceptor ?
2p
10.7 ev


HOMO
The highest occupied molecular orbital (HOMO) of CO is
weakly antibonding (compared with the O atomic orbitals)
and is an MO which is carbon based. Secondly, the *
antibonding orbital which is the lowest unoccupied molecular
orbital (LUMO) is also of comparatively lower energy which 2p
15.9 ev
makes it possible to interact with metal t2g orbitals for 
bonding. There exists a strong back bonding of metal 
electrons to the  * antibonding orbitals of CO

2s *
19.5 ev

 2s
32.4 ev
C CO O
Stabilizing Low Oxidation State: CO Can Do the Job

Ni(CO)4], [Fe(CO)5], [Cr(CO)6], [Mn2(CO)10],

[Co2(CO)8], Na2[Fe(CO)4], Na[Mn(CO)5]
 Synthesis of Metal Carbonyls

Direct carbonylation

Reductive carbonylation
 18 electron rule : How to count electrons
The rule states that thermodynamically stable transition metal organometallic compounds are formed when
the sum of the metal d electrons and the electrons conventionally considered as being supplied by the
surrounding ligands equals 18.

1920 British Chemist Sidgwick

Organic compounds – Octet rule

Organometallic – 18 electron rule

18 valance electron – inert gas configuration

In general, the conditions favouring adherence to the 18

electron rule are, an electron rich metal (one that is in a low
oxidation state) and ligands that are good -acceptors
Octet rule
 Counting the number of electrons
Neutral atom method
Ligand Name Bonding Type Formal Electrons
Charge donated
H
Molecular Hydrogen: H2 M 0 2
H

Hydride H- M-H -1 1

Halide X- M-X -1 1

Amine, phosphine, M-NR3 M-PR3 0 2

arsine: NR3, PR3, AsR3

Carbonyl: CO M C O 0 2

Alkyl , Aryl M-CR M-Ph -1 1

Alkene M 0 2
H2C CH2
Methods of counting: Neutral atom method & Oxidation state method
Ligand Neutral Oxidation state Ligand Neutral Oxidation state
atom atom
Electron Formal Electron Formal
contributi charge contribu charge
on tion
Carbonyl (M–CO) 2 2 0 Halogen ( M–X) 1 2 –1
Phosphine (M–PR3) 2 2 0 Alkyl (M–R) 1 2 –1
Amine (M–NR3 ) 2 2 0 Aryl (M–Ar) 1 2 –1
Amide (M–NR2 ) 1 2 –1 acyl (M–C(O)–R 1 2 –1
Hydrogen (M–H) 1 2 –1 1-cyclopentadienyl 1 2 –1
Alkene (sidewise) 2- 2 2 0 1-allyl 1 2 –1
Alkyne (sidewise) 2- 2 2 0 3-allyl 3 4 –1
2-C60 2 2 0 5-cyclopentadienyl 5 6 –1
Nitrosyl bent 1 2 –1 6-benzene 6 6 0
Nitrosyl linear 3 2 +1 7-cycloheptatrienyl 7 6 +1
Carbene (M=CR2) 2 4 –2 Carbyne (MCR) 3 6 –3
Alkoxide (M–OR) 1 2 –1 Thiolate (M–SR) 1 2 –1
-CO (M–(CO)–M) 2 2 0 -H 1 2 –1
-alkyne 4 4 0 -X (M–X–M) 3 4 –1
X = halogen
-alkyl 1 2 –1 -amido 3 4 –1
(M–(NR2)–M
-phosphido 3 4 –1 -alkoxide 3 4 –1
(M–(PR2)–M (M–(OR)–M
Neutral atom method: Metal is taken as in zero oxidation state for counting purpose

Oxidation state method: We first arrive at the oxidation state of the metal by considering the number of
anionic ligands present and overall charge of the complex

Neutral atom method

[Mn(CO)5] -

Mn 7e 2Rh 9+9 = 18
5CO 10 4CO 4x2 8
Charge 1e 2Cl(bridging) 2x3 6
------------------------------ -----------------------------------------
[Mn(CO)5] - 18 e Rh2(CO)4Cl2 32 or 16e/Rh

Suggestion: Focus on one counting method till you are confident

Ph3P PPh3
Rh Rh is s1d8 = 9e
Ph3P Cl
since Cl is -1, Rh is +1 (the complex is neutral)

9e - 1e + 8e = 16e 4 ligands x 2e each = 8e

therefore coordinately unsaturated

 neutral atom oxidation state
method method
CO Ru 8 6 (Ru +2)
PPh3
Ru 3- allyl 3 4
2 PPh3 4 4
PPh3
CO 2 2
charge -1 not required
16 16
Me
N Fe 8 6 (Fe +2)
Me
Fe 2 5-Cp 10 12
18 18

Metals having odd number of electrons cannot satisfy the 18-electron rule by simple addition of
CO (or other two electron donors) ligands because the resulting moiety will necessarily also have
an odd number of electrons. Mn(CO)5 and Co(CO)4 – 17 electrons – do not exist, corresponding
anoins [Mn(CO)5] - and [Co(CO) 4]- are stable
Easy way to remember ligand electron contribution for neutral atom counting method
Electron contribution
Neutral terminal : CO, PR3, NR3 2 electrons
Anionic terminal : X-, H-, R-, Ar-, R2N-, R2P-, RO- 1 electron
Hapto ligands : 2-C2R4 2-C2R2, 4-C2R2 ,1-allyl,
3-allyl, 4- Cb, 5-Cp, 6-C6H6
7-C7H7 8-C8H8 2-C60, 5-R5C60 same as hapticity

NO linear 3 electrons

NO bent ( l. p on nitrogen) 1 electron

Carbene M=C 2 electron

Carbyne MC 3 electron

 d d d d d d d d d s
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
 Exceptions to the 18 electron rule

• Square planar organometallic complexes of the late transition metals (16e).

• Some organometallic complexes of the early transition metals (e.g. Cp2TiCl2,

WMe6, Me2NbCl3, CpWOCl3) [ A possible reason for the same is that some of the orbitals of these complexes
are too high in energy for effective utilization in bonding or the ligands are mostly  donors.]

• Some high valent d0 complexes have a lower electron count than 18.

• Sterically demanding bulky ligands force complexes to have less than 18 electrons.

• The 18 electron rule fails when bonding of organometallic clusters of moderate to

big sizes (6 Metal atoms and above) are considered.

• The rule is not applicable to organometallic compounds of main group metals as

well as to those of lanthanide and actinide metals.
 Catalysis

Catalyst
A+B C Cat al yzed r xn
pr oceedi ng t hr ough
an i nt er m edi at e

Ea

A catalyst typically increases the reaction rate Ea

by lowering the activation barrier for a G catalyzed
transformation, by introducing a new
Reactants
reaction pathway. G

Products

It does not change the thermodynamics!! Reaction Coordinate

Heterogeneous Homogeneous
 Catalysis : Why?

Synthesis of chemicals… pharmaceutical, agricultural

Catalytic converter … environmental

Biology: Enzymes

Biological system – efficient catalyst

Organometallic compounds, metals etc.

 The three-way catalytic converter first separates
the NOX into nitrogen and oxygen and then
converts the HC and CO into harmless water (H2O)
and carbon dioxide (CO2).

Heterogeneous
Catalytic Converter
 How to select an efficient catalyst?
Activity: related to rate of reaction (also called turnover)
efficient catalyst: good activity

Turnover frequency (f) f = /[Q] Q - catalyst

Large turnover frequency – efficient catalyst

Selectivity: Byproducts should be minimized

Lifetime: It is costly to replace the catalyst frequently

Cost: The acceptable cost depends upon the catalyst lifetime, product value
lifetime and product value

Poisoning: decomposition of catalyst, adsorption of reactant/product

 Comparing different catalysts; Catalyst life and Catalyst efficiency

Turnover Number (TON)

TON is defined as the amount of reactant (in moles) divided by the amount of catalyst (in moles) times the
percentage yield of product. A large TON indicates a stable catalyst with a long life.

turnover number is the number of cycles for which a catalyst survives

Turnover Frequency (TOF)

It is the number of passes through the catalytic cycle per unit time (often per hour). Effectively this is
dividing the TON by the time taken for the reaction. The units are just time–1 . A higher TOF indicates better
efficiency for the catalyst
 Coordination compounds in catalysis
Nobel Prizes

2005 Yves Chauvin, Robert H. Grubbs

and Richard R. Schrock.
2001 KNOWLES, NOYORI, SHARPLESS
1973 WILKINSON
1963 ZIEGLER, NATTA
1918 HABER
1909 OSTWALD
 Catalytic steps

(a) Ligand coordination and dissociation

(b) Oxidative addition
(c) Migratory insertion
(d) Nucleophilic attack
(e) Reductive elimination
Ligand coordination and dissociation:

Facile coordination of the reactant and facile loss of products.

Coordinatively unsaturated - 16-electron complexes

Oxidative addition

When addition of ligands is accompanied by oxidation of the metal, it is called an oxidative addition reaction

LnM + XY Ln(X)(Y)M
dn dn-2
OX state of metal increases by 2 units Mn to Mn+2
Coordination number increases by 2 units H
H2 oxidative
Ph3P PPh3 addition H PPh3
2 new anionic ligands are added to the metal Rh Rh
Ph3P Cl Ph3P Cl
Requirements for oxidative addition PPh3
+1 +3
Rh Rh
• availability of non-bonded electron density on the metal,

• two vacant coordination sites on the reacting complex (LnM), that is, the complex must be coordinatively unsaturated,

• a metal with stable oxidation states separated by two units; the higher oxidation state must be energetically accessible
and stable.
Oxidative addition…

X-Y X
+ X-Y LnMn+2
LnMn
LnMn Y

Ph3P Cl
Ir + H2
Ph3P CO
Examples of Oxidative addition : Cis or trans ?

Homonuclear systems (H2, Cl2, O2, C2H2) Cis

Heteronuclear systems (MeI) Cis or trans
An important step in many homogeneous catalytic cycles
Hydrogenation of alkenes- Wilkinson catalyst
H
H2 oxidative

Often the first step of the mechanism

Ph3P PPh3 addition H PPh3
Rh Rh
Ph3P Cl Ph3P Cl
PPh3
Rh+1 Rh+3

Methanol to acetic acid conversion- Cativa process

CH3
I CO CH3I I CO
Ir Ir
I CO I CO
Ir+1 Ir+3 I

The more electron rich the metal, more easy is the oxidative addition
 Migratory Insertion
X L
+L
M Y [M-Y-X] M Y X
dn dn

No change in the formal oxidation state of the metal

A vacant coordination site is generated during a migratory insertion (which gets occupied by the incoming ligand)
The groups undergoing migratory insertion must be cis to one another

CH3 Ph3P O
OC OC
CO C
Mn + PPh3 Mn CH3
OC CO OC CO
OC OC

These reactions are enthalpy driven and although the reaction is entropy
prohibited the large enthalpy term dominates
 Types of Migratory Insertion

CO O
CH2CH2R 1, 1-migratory Ph P CCH2CH2R
Ph3P insertion 3
Rh Rh
OC PPh3 OC PPh3

H
R 1, 2-migratory CH2CH2R
Ph3P
Ph3P insertion
Rh Rh
Ph3P OC PPh3
CO
Migratory insertion
Migration of alkyl and hydride ligands

R L R
L+ M CO M C
O

H CH
2
M M CH2CH3
CH2
 S

LnM CR

O
S

L'
R L' LnM CR
LnM LnM CR
C O
O
O

R
C
LnM O
 (d) Nucleophilic attack

R R 2+ H R +
C
L3Pd C C OH
L3Pd OH2
C R R
H R

-
O
L5M - -
CO + OH L5M C OH L5M H
+
CO2
 Reductive elimination

Almost the exact reverse of Oxidative Addition

CH3 Ph2
Ph2
P CH3 P CH3
reductive elimination + H3C CH3
Pt Pt
165 °C, days P CH3
P CH3
Ph2 Ph2
CH3
Pt4+ Pt2+

Oxidation state of metal decreases by 2 units

Coordination number decreases by 2 units
2 cis oriented anionic ligands form a stable  bond and leave the metal

Factors which facilitate reductive elimination

• a high formal positive charge on the metal,

• the presence of bulky groups on the metal, and
• an electronically stable organic product.

Cis orientation of the groups taking part in reductive elimination is a MUST

 Reductive elimination
Hydroformylation ( conversion of an alkene to an aldehyde)

Cativa Process (Methanol to Acetic acid)

Hydrogenation of Unsaturated Hydrocarbons

H H
-CH=CH- + H2 → -CH-CH-

NOBEL : 1973

The most common catalyst


Wilkinson’s Catalyst, [RhCl(PPh3)3]
 Wilkinson’s Catalyst (WC)

Ph 3P PPh 3

Rh

Cl PPh 3
Chlorotris(triphenylphosphine)rhodium(I)
square planar d8 configuration
 Geoffrey Wilkinson
• Born July 14, 1921, Yorkshire, England
• Ph.D from Cal Berkeley studying with Glenn Seaborg
• First published compound in 1965 in Journal of the Chemical Society - Chemical
Communications
•Nobel Prize in Chemistry 1973 (shared with Ernst Otto Fischer) for their pioneering
work, performed independently, on the chemistry of the organometallic, so called
sandwich compounds.

Organometallic compounds prepared by

Wilkinson in display at Harvard Univ.
 Synthesis of WC
Ph 3P PPh 3
EtOH
RhCl3 + 3 H2O + >4 PPh3 Rh + Ph3PO
78 oC
Cl PPh 3

Commercially available
 WC in alkene Hydrogenation: Catalytic Steps
(1) Oxidative addition

H
Ph3P PPh3 Ph3P PPh3
Rh + H2 Rh
Ph3P Cl Ph3P H
Rh+1 Cl
Rh3+
(2) Ligand Dissociation

H H
Ph3P PPh3 Ph3P
Rh Rh H + PPh3
Ph3P H Ph3P
Cl Cl
 WC in alkene Hydrogenation: Catalytic Steps
(3) Ligand Association

H H CH2
Ph3P H H
Ph3P CH2 Ph3P Rh
Rh H + Rh CH2
PPh3
Ph3P CH2 Ph3P Cl H
Cl
H2CCl CH2
(4) Migration/Insertion

H H CH2
Ph3P H CH
H 2
Ph3P Rh CH2
Cl Rh
CH2
PPh Ph3P
3
Ph3P H Rh H
H2CCl CH2 Ph3P
Cl
 WC in alkene Hydrogenation: Catalytic Steps

(5) Ligand association

H CH2 H CH2
CH2 CH2
Ph3P Ph3P PPh3
Rh H + PPh3 Rh
Ph3P Ph3P H
Cl Cl
 WC in alkene Hydrogenation: Catalytic Steps

(6) Reductive elimination

H CH2
CH2
Ph3P PPh3 Ph3P PPh3
Rh Rh
Ph3P H Ph3P + CH3 CH3
Cl
Cl

(note: regeneration of the catalyst)

 WC in alkene Hydrogenation: Additional Notes

Rate of the reaction decreases as the alkyl substitution increases

Highly sensitive to the nature of the phosphine ligand
Analogous complexes with alkylphosphine ligands are inactive
Highly selective for C=C over C=O

Applications

* Laboratory scale organic synthesis

* Production of fine chemicals
?
 Alkene Hydrogenation & Chirality

Chiral phosphine ligands have been developed to synthesize optically active products.
Synthesis of L-DOPA (Used in the treatment of Parkinson’s diseases)
Synthetic route was developed by Knowles & co-workers at Monsanto

Dr. William S. Knowles received Nobel prize in chemistry 2001 along with other two
scientists.
This reaction, developed by Knowles, Vineyard, and Sabacky, was used at
Monsanto as a commercial route to the Parkinson's drug L-DOPA.
 Acetic Acid
➢ Acetic acid is an important industrial chemical
➢ Over 8 million tonnes is produced all over the world
annually
 Synthesis of Acetic Acid

The traditional synthesis uses bio-oxidation of ethanol

obtained via fermentation:
C6H12O6 → 2 C2H5OH + 2 CO2
C2H5OH + O2 → CH3COOH + H2O
This is not a clean and efficient process!

Industrial acetic acid synthesis:

CH3OH + CO → CH3COOH
Catalyzed by a rhodium complex.