Organic and Inorganic Chemistry

CYN-002
B. Tech I Yr. Courses

Dr. Dheeraj Kumar

1
2
 Prof. Yadagiri
Dongari

Prof. R K Peddinti

Prof. Dheeraj
Kumar

3
Coordination Chemistry

4
5
 ORGANOMETALLIC CHEMISTRY
An area which bridges organic and inorganic chemistry
A branch of coordination chemistry where the complex has one or more metal-
carbon bonds

➢ The 18 electron rule

➢ Factors affecting M-C bond formation

➢ Metal carbonyls – synthesis, reactions and structures

➢ Transition metal-π alkene complexes-synthesis, reactions, bonding and

stability

➢ Applications of organometallic compounds in catalytic processes:

hydroformylation, hydrogenation, catalytic decarbonylation, olefin

metathesis and enantioselective hydrogenation of alkenes

6
 Organometallic Compounds

Ferrocene
C always more electronegative compared to M

An "organometallic" compound is 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.

• Traditional chemists do not agree for classifying metal cyanide

complexes as organometallic
• Many consider Wilkinson’s Catalyst as organometallic even
though such molecule lack the required M-C bond. Wilkinson’s Catalyst
7
 Applications of Organometallic Compounds
Uses of organometallic compounds: Homogeneous catalyst in
industrial processes, Synthetic Precursors, Pharmaceuticals,
Agrochemicals, Flavors, Fragrances, Semiconductors and Ceramic
precursors.
Organometallic compounds provide a source of
nucleophilic carbon atoms which can react with
electrophilic carbon to form a new carbon-carbon
bond. This is very important for the synthesis of
complex molecules from simple starting materials.

❑ Olefin Metathesis

Nobel Prize – 2005 : Robert H.

Grubbs and Richard R. Schrock

❑ Metal catalysed cross coupling reactions

Nobel Prize – 2010 : Richard F. Heck, Ei-ichi Negishi, Akira Suzuki for their work
in palladium-catalyzed coupling reactions in organic synthesis 8
 Zeise’s Salt - The first transition metal organometallic compound

Discovery 1827
Structure ~ 150 years later
W C Zeise, Danish
pharmacist, I789- I847 Potassium trichloro(ethylene)platinate(II)

Diethyl zinc - First  bonded Organometallic Compound

3 C2H5I + 3 Zn → (C2H5)2Zn + C2H5ZnI + ZnI2

Frankland coined the term “Organometallic”

Prepared diethyl zinc while trying to make ethyl radicals.

Edward Frankland
1825-1899
9
Hapto ligands and Sandwich compounds

The hapto symbol, , with a numerical superscript, provides a

topological description by indicating the number of carbon atoms at a
bonding distance to the metal

(5-C5H5)2Fe (6-C6H6)2Cr
G. Wilkinson E. O. Fischer
The Nobel Prize in Chemistry 1973 was awarded jointly to Ernst Otto Fischer and Geoffrey Wilkinson "for their
pioneering work, performed independently, on the chemistry of the organometallic, so called sandwich compounds

Bent Sandwich Half Sandwich Triple decker &

polycyclic

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10
11
 Bridging Ligands
• In coordination chemistry, a bridging ligand is a ligand that connects two or
more atoms, usually metal ions.

• In naming a complex wherein a single atom bridges two metals, the bridging
ligand is preceded by the Greek letter mu, μ, with a subscript number denoting
the number of metals bound to the bridging ligand. μ2 is often denoted simply
as μ.

• Ligands that are not bridging are called terminal ligands.

two chloride ligands are terminal cluster [Au6C(PPh3)6]2+

and two are μ2 bridging. μ3-chloride ligand features a μ6-carbide ligand

12
 18 Electron Rule
When the metal achieves an outershell configurations of
ns2(n-1)d10np6, there will 18 electron in the valence orbitals
and a closed stable configuration.
This rule of thumb is called “18 electron rule”

According to this rule, in a complex, the sum of metal

valence electrons and the electrons donated by the ligands
is 18. It provides a closed and stable configuration, ns2(n-
1)d10np6.

e.g. Cr(CO)6, [Fe(CN)6]4−, Ni(CO)4, Mn2(CO)10, Co2(CO)8,

HMn(CO)5

All 18 electron organometallic compounds are generally Stable

13
Methods of counting: Neutral atom method & Oxidation state method
Ligand Neutral Oxidation state Ligand Neutral Oxidation state
atom atom
Electron Formal Electron Formal
contribution charge contributi charge
on
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
Thiocarbonyl (M-CS) 2 2 0 Isocyanide (M-CNR) 2 2 0
14
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 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

Suggestion: Focus on one counting method till you are confident

15
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
bridging neutral 2-CO, 3-CO 2 electrons
Bridging anionic 2-CH3, 2-H ( no lone pairs) 1 electron

Bridging anionic 2-Cl, , 2-OR, 2-PR2, 2-NR2 3 electrons

(with 1 lone pair)
3-Cl( 2 l.p) 5 electrons

Bridging alkyne 4 electrons

NO linear 3 electrons

NO bent ( l. p on nitrogen) 1 electron

Carbene M=C 2 electron

Carbyne MC 3 electron

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Valence Electrons Calculation

17
17
18-electron Rule: Illustrative Examples

18
 Q1) Consider the 18 electron rule as a guide and determine the value of n in
the following complexes.
(a) Na2Fe(CO)n
(b) MnBr(CO)n
(c) W(η6-C6H6)(CO)n
(d) Rh(η5-C5H5)(CO)n
(e) Cr(η3-C5H5)(CO)n(CH3)
(f) IrBr2(CO)n(CH3)

Q2)

Ans 1. (a) n = 4, (b) n = 5, (c) n = 3, (d) n = 2, (e) n = 4, (f) n = 1

Ans 2. (a) x = 2, (b) x = -3, (c) x = +1, (d) x = +1, (e) x = 0, (f) x = +1 19
Q3)

Q4)

Ans 3. A = Ni, B = Co, C = Mn

Ans 4. (a) NO is linear; (b) NO is bent, and (a) will have shorter M-N bond as three
electrons are donated to Ru. 20
 How to determine the total number of metal - metal bonds ?
Determine the total valence electrons (TVE) in the entire molecule (that is, the number of
valence electrons of the metal plus the number of electrons from each ligand and the
charge); say, it is A.

Subtract this number from n × 18 where n is the number of metals in the complex, that is, (n
× 18) – A; say, it is B.

(a) B divided by 2 gives the total number of M–M bonds in the complex.

(b) A divided by n gives the number of electrons per metal. If the number of electrons is 18, it
indicates that there is no M–M bond; if it is 17 electrons, it indicates that there is 1 M–M
bond; if it is 16 electrons, it indicates that there are 2 M–M bonds and so on.

Molecule TVE (18 × n) – A Total M–M Bonds per metal Basic geometry of
(A) (B) bonds (B/2) metal atoms

Fe3(CO)12 48 54 – 48 = 6 6/2 = 3 48/3 = 16; 2 Fe Fe

Fe
Co
Co4(CO)12 60 72 – 60 = 12 12/2 = 6 60/4 = 15; 3
Co Co

Co

[η5-CpMo(CO)2]2 30 36 – 30 = 6 6/2 = 3 30/2 = 15; 3 Mo≡Mo

(4-C4H4)2Fe2(CO)3 30 36 – 30 = 6 6/2 = 3 30/2 = 15; 3 Fe≡Fe

Fe2(CO)9 34 36 – 34 = 2 2/2 = 1 34/2 = 16; 1 Fe–Fe

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 A few worked out examples

Understanding metal –metal bond electron count become easier if you

compare and see how octet is attained by each Cl atom of Cl2 22
23
 METAL CARBONYLS
CO CO CO

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 OC Co Co CO
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 Heteroleptic Carbonyls
OC CO
CO CO

Homoleptic Carbonyls
• Carbonyl is one of the most important ligand in organometallic chemistry.
• Homoleptic Carbonyls (complexes containing only carbonyls as ligands)
• 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. It exist as V(CO)6ˉ
• Most of the metal carbonyls have metal in very low oxidation state, sometime even zero and negative24
oxidation state.
 Why study metal carbonyls ?
• Simplest of organometallic compounds where M-C  bonding is well
understood. CO is one of the strongest  acceptor ligands.

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

Hydroformylation Methanol to Acetic acid Process
Alkene to Aldehyde
R
(MONSANTO PROCESS)
C CH2
H MeOH + HI MeI + H2O

CO, CO H3C C I
HCo(CO)4 MeI
H2
[Rh(CO)2I2] O
R H2O
CH CH2 H3C C I H3C C OH
H HC O O
O
• Back bonding ( bonding) and variation in electronic properties of CO can
be monitored very efficiently by Infrared spectroscopy.

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 Molecular Orbital diagram of CO
*

Why does CO bind a metal through its less

electronegative carbon atom? What makes *

it a good  acceptor ? LUMO

✓ The highest occupied molecular orbital 2p

(HOMO) of CO is weakly antibonding 10.7 ev

(compared with the O atomic orbitals) HOMO
and is an MO which is carbon based.
✓ The * antibonding orbital which is the
lowest unoccupied molecular orbital
(LUMO) is also of comparatively lower 2p
energy which makes it possible to 15.9 ev

interact with metal t2g orbitals for 


bonding.
✓ There exists a strong back bonding of *
2s
metal electrons to the  * antibonding 19.5 ev

orbitals of CO.
Bond order = ½(Nb – Nab) = ½ (8-2) = 3  2s
32.4 ev
C CO O
CO is a very good σ donor as well as a good π acceptor. 26
 Orbital Overlap for  and  bonding in
metal carbonyls

First two electron donation of the lone pair on carbon into a vacant metal d-orbital
( donation). This electron donation makes metal more electron rich, and in order
to compensate for this increased electron density, a filled metal d orbital can
interact with empty π* orbital of the carbonyl ligand to relieve itself of the added
electron density (π back bonding).
27
 Synergic Bonding in Metal Carbonyls

• The two components of this bonding are synergistic. The more sigma
donation by the carbonyl (or other sigma-donors on the metal center),
the stronger the pi-backbonding interaction.

• As the electron density on a metal center increases, more -back-

bonding to the CO ligand(s) takes place. This weakens the C-O bond by
pumping more electron density into the formally empty carbonyl *
orbital. This increases the M-CO bond strength making it more double-
bond-like, i.e., the resonance structure M=C=O assumes more
importance.
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 Extent of Backbonding in Metal Carbonyls

(No Back Bonding) (Full Back Bonding)

Real Metal carbonyls are in between these two structures (extremes).

• IR Spectroscopy (CO) and crystal structure (M-C bond length) will give
information will give idea about the structure.

29
 Infrared Spectroscopy- A spectro-analytical tool in chemistry

Useful For Functional Group Determination

Infrared (IR) spectroscopy is one of the most common spectroscopic techniques used by organic
and inorganic chemists. Simply, it is the absorption measurement of different IR frequencies by a
compound positioned in the path of an IR beam. The main goal of IR spectroscopic analysis is to
determine the chemical functional groups in the sample. Functional groups are identified based
on vibrational modes of the groups such a stretching, bending etc. Different vibrational modes
absorb characteristic frequencies of IR radiation. An infrared spectrophotometer is an
instrument that passes infrared light through a molecule and produces a spectrum that contains
a plot of the amount of light transmitted on the vertical axis against the wavelength of infrared
radiation on the horizontal axis. Absorption of radiation lowers the percentage transmittance
value. 30 30
 Stretching Frequency in IR Spectroscopy

Stretching frequency (ν) is directly proportional to k ( depend on the bond strength).

The bonding in the carbonyl to the metal is highly sensitive to electronic
effects of the metal centre. This is usually monitored by IR Spectroscopy.

M C O M C O
 CO Higher  CO Lower
More back bonding

31
✓ Co2(CO)8 has two isomers one with no bridging carbonyls
and other with two bridging carbonyl groups, both also being
18 electron species (How to differentiate?).
✓ As the C-O bond stretching frequency is quite sensitive to
small changes in the electronic environment, one can identify
these by IR spectral studies.
✓ The C-O stretching frequencies of terminal carbonyls come
in the range of 2125 - 1850 cm-1 while bridging carbonyl
stretching frequencies come in the range of approximately
1850 - 1700 cm-1.
32
 Terminal versus bridging carbonyls
O
M O
C
C
C M
M M M
O
M
terminal bridging  2 bridging 
 3
CO 2120-1850 cm-1
1850-1700 cm-1 1730-1620 cm-1
Cp
CO Fe CO

OC CO
Cr OC Fe Cp
OC CO OC Fe
Cp
CO

2000 cm-1 2018, 1826 cm-1 Fe CO

Cp

termial bridging 1620 cm-1

Bridging CO groups can be regarded as having a double bond C=O group, as compared
to a terminal CO, which is more like a triple bond.
33
Infrared Spectroscopy- Spectra of Metal Carbonyls

CO OC CO
OC

OC Mn Mn CO
The range in which
OC CO the band appears
CO OC
decides bridging or
terminal terminal .

The number of
bands is only
related to the
symmetry of the
O
C
O
C
bridging molecule
OC CO

OC Fe Fe CO
OC C CO
O

terminal

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 Factors which affect CO stretching frequencies
Variation in CO (cm–1) of the first row transition 1.Charge on the metal
metal carbonyls 2. Effect of other ligands
free CO
2143 As the electron density on a
Ni(CO)4 d8 metal centre increases,
2057
more -backbonding to the
Co(CO)4- Co2(CO)8 CO ligand(s) takes place.
1890
d8 2044(av, ter)
This weakens the C–O bond
[Fe(CO)4]2- Fe(CO)5
1815
d8 2030
further as more electron
density is pumped into the
[Mn(CO)4]3- Mn(CO)6 + Mn2(CO)10
1600,1790 d8 2098
d4 2013 (av) empty * anti-bonding
[Cr(CO)4]4- Cr(CO)6
carbonyl orbital. This
d4 increases the M–C bond
1462,1657 2000
V(CO)6¯ V(CO)6 order and reduces the
d4
1860 1976 C-O bond order. That is, the
Ti(CO)62- resonance structure M=C=O
d4
1747 becomes more dominant.

M C O M C O
 CO Higher  CO Lower
35
More back bonding
 Effect of other ligands trans to CO
Effect of different Co-ligands on CO (cm-1) of Mo(CO)3L3

Complex  CO cm–1
(fac isomers)
Mo(CO)3(PF3)3 2090, 2055
CO
Mo(CO)3(PCl3)3 2040, 1991 More back bonding =
L CO
Mo Mo(CO)3[P(OMe)3]3 1977, 1888 More lowering of
L CO the C=O bond order =
Mo(CO)3(PPh3)3 1934, 1835
L More lower  CO
Mo(CO)3(NCCH3)3 1915, 1783 stretching frequency
Mo(CO)3(dien)* 1898, 1758
Mo(CO)3(Py)3 1888, 1746

The better the  donating capability of the other ligands on the metal, more electron
density given to the metal, more back bonding (electrons in the antibonding orbital of
CO) and lower the CO stretching frequency.
Based on CO IR stretching frequencies, the following ligands can be ranked from
best -acceptor to worst:

NO > CO > PF3 > RNC > PCl3 > P(OR)3 > PR3 > RCN > NH3 36
 Problems
1. The V-C bond length in V(CO)6- and V(CO)6 are 1.93 and 2.00 A°respectively.
Justify the bond lengths.
2. In a carbonyl complex with linear CO-M-CO group, how will CO change when a)
one CO is replaced by Et3N b) a positive charge is put on the complex c) a
negative charge is placed on the complex.
3. Arrange the following in the decreasing order of back donation
Cr(CO)6; [Ti(CO)6]-2 ; [Mn(CO)6]+ ; [Ir(CO)6]3+; [V(CO)6]-

4. Which of the following complexes will show a lower carbonyl stretching

frequency. Give reasons for your answer.

Cp Cp
Cl CO
Zr Zr
CO CO
Cp Cp
A B
37
 Problems
Q1. Select the best choice in each of the following and briefly justify the reason for your choice
a) Complex with the shortest C-O bond
Ni(CO)4, [Co(CO)4]-, [Fe(CO)4]2-
b) Complex with the lowest C-O stretching frequency
Cr(CO)6 V(CO)6- Fe(CO)62+
Q2. Which one of the following complexes (a) and (b) will undergo ligand substitution faster with
PPh3? Why?
(a) V(CO)6 (b) [V(CO)6] ̶
Q3. The compound (ƞ5-C5H5)Co(CO)2 (A) upon UV irradiation, resulted in the evolution of a gas and
formation of a new compound, B. While the infrared spectrum of A showed absorptions around
1988 cm-1, the spectrum of B showed absorptions only at 1788 cm-1. Compounds A and B obey the
18 electron rule and both have cyclopentadienyl group in the ƞ5 mode. Draw the structure of
compounds B.
Q4. The compound Re(CO)5Br upon UV irradiation resulted in the evolution of an
equimolar amount of a colourless gas and the formation of a new stable complex X.
The infrared spectrum of compound X indicated the absence of metal-metal bond and
showed bands in the range of 2040-1965 cm-1. The starting material Re(CO)5Br also
showed bands in the same spectral range. Draw the structure of compound X.
Q5. In the given pair of complexes pick out the complex having lower energy CO stretching
frequency in its infrared spectrum. Rationalise your choice.
(a) Mo(CO)6 and Mo(CO)5PPh3 (b) Fe(CO)5 and Fe(CO)4Br2

38
 Answers
1 : (a) Shortest CO bond Ni(CO)4 (b) Lowest CO stretching V(CO)6-.
2 : The mechanism of ligand substitution is different in both cases. V(CO)6 is a 17 e
system and it will prefer ligand substitution by an associative mechanism.
However [V(CO)6] ̶ is an 18 e coordinatively saturated complex and it will undergo
ligand exchange by a dissociative mechanism. Since CO is more tightly bound in
[V(CO)6] ̶ {higher back donation}, [V(CO)6] ̶ will be less reactive than V(CO)6.
3 : Infrared absorption of B indicates only
bridging carbonyls. To attain 18 electrons,
dimerization will take place with the
formation of a Co-Co double bond.
4 : The colourless gas has to be CO as bromine vapours are
coloured. Equimolar amount means one CO is released per
Re(CO)5Br; 2040-1965 cm-1, is the terminal carbonyl region.
Based on this and absence of metal-metal bonds, the structure
is one with bridging bromines
5 : (a) Mo(CO)5PPh3 will have lower CO since PPh3 is a poorer π acceptor ligand
than CO.
(b) Fe(CO)4Br2 [Fe2+ = 3d6]; Fe(CO)5 [Fe = 3d64s2]. Since the electron density on Fe0
is higher, back donation to CO will be more. Hence Fe(CO)5 will have lower CO .
39
NO > CO > PF3 > RNC > PCl3 > P(OR)3 > PR3 > RCN > NH3
40
 (REDUCTIVE CARBONYLATION)

(CO itself acts as a reducing agent and get converted to CO2 in the process.
The reaction conditions are relatively more drastic for such reactions)

41
 Reactions of Metal Carbonyls

1. Reduction : Carbonyl anions

V(CO)6 + Na Na[V(CO)6]

Mn2(CO)10 + 2Na 2 Na[Mn(CO)5]

Co2(CO)8 + 2Na 2 Na[Co(CO)4]

Fe(CO)5 + Na/Hg Na 2Fe(CO)4

2. Oxidation : Iodocarbonyls
Mn2(CO)10 + I2 2 Mn(CO)5I

Fe(CO)5 + I2 Fe(CO)4I2

3. Photochemical substitution
h W(CO)5(PPh3) + CO
W(CO)6 + PPh3
In the presence
Fe(CO)5 + h of UV radiation
Fe(CO)3 + 2CO
a monodentate
ligand displaces
only one CO unit

42
43
 PROPERTIES OF CARBONYL HYDRIDES

The term hydride is assigned based on the formal oxidation state, however, the
properties of organometallic hydrides vary from hydridic to protic in character.

The carbonyl hydrides of transition metals behave as both acid as well

as base. The strong π-acceptor ligands such as CO have strong
electron withdrawing character and leads to the polarization of the M-H
bond in HM(CO)n complexes.

Based on the nature of metal and ligands, the acidity of these complexes varies significantly.

• The acidic character of metal carbonyl hydrides decreases on descending the group in
periodic table.
• Bridging hydrides are more acidic than complexes with terminal M-H.
• The σ-donor ligands such as Cp, phosphines, etc. reduce the acidity of M-H bond,
whereas, π-acceptor ligands such as CO, NO, PF3 increases the acidity of M-H bond.

HCo(CO)3(PMe3) < HCo(CO)3(PPh3) < HCo(CO)3(PF3)

44
 Reactions of Metal Carbonyls

6. Nucleophilic addition to CO
R OLi R OCH3
CO
C C
OC CO OC
OC CO [Me3O]BF4 CO
W RLi W
W
OC CO OC
ether OC CO CO
OC OC
OC
Fischer Carbene
Carbenes are catalysts
for olefin metathesis
Et
Et
Al
7. Migratory insertion of CO O
Et
O CO CO
2 AlEt3
C Me C
Me
Fe Fe Fe OFe
CC
C OC
OC OC OCO O
CO
OC CO
Mn Et AlMn
OC CO high pressure Et Et
OC CO
OC
OC

45
Photochemical Substitution
Photochemical substitutions are the most common photoreactions in organometallic chemistry.
Kinetic studies have shown that the rate constant for the dissociation of one CO unit which
precceds the entrance of a new ligand is increased upon photochemical excitation by a factor of
1016. h
W(CO)6 + PPh3 W(CO)5(PPh3) + CO

Fe(CO)5 + h
Fe(CO)3 + 2CO

Photochemical excitation of a metal carbonyl with a mixed substituent coordination sphere causes dissociation
of a ligand which is most weakly bonded in the ground state as well. If ligands of comparable ligand strength
are used one can displace all the carbonyl groups

If after dissociation of a ligand no suitable free ligands are present the free coordination site generated
through photochemical dissociation of CO may get closed by dimerization. The gap may also be filled internally
by an 1 to 3 rearrangement
Br
h
2 Re(CO)5Br (CO)4Re Re(CO)4
Br
Mn(CO)5 h
- CO Mn(CO)4
46 46
 Alkene and Alkynes As Ligands
Zeise’s Salt - The first transition metal organometallic compound

Discovery 1827
Structure ~ 150 years
W C Zeise, Danish later
pharmacist, I789- I847 Potassium trichloro(ethylene)platinate(II)

• Ethylene molecule occupies the 4th coordination site of square planar complex with
its C-C axis perpendicular to the platinum-ligand plane.

• Alkene can bind to metal center and act as both σ donor and π acceptor.

• Relative to the free ethylene, the C-C bond in the complex is lengthened slightly and
the hydrogens are slightly tilted back from the planar arrangement.

47
 Models of Ethylene-Metal Bonding
• Two Models: Dewar-Chatt-Duncanson Model
and Metallacyclopropane Model.
• Structural studies on a large number of alkene
complexes have shown that they fall in between
M M
these two extremes depending on the M and
Dewar-Chatt cyclopropane
substituents on the alkene carbon atoms.

For Zeise’s salt, the best bonding picture is given by the Dewar-Chatt-Duncanson
model. This involves the donation of the C=C  electrons to an empty d sigma
orbital of the metal, accompanied by back donation from a filled metal d orbital
into an empty C=C * orbital.

C C
M  M *
C C

donation from  back donation to *

Dewar- Chatt - Duncanson Model
As the back donation for the metal is important to stabilize the complex only soft
metals capable of back donation binds alkenes. 48
Bond distances of few platinum-alkene complexes
Pt(+2) Pt(0) Pt(+2)

(Zeise’s Salt)

Dewar-Chatt-Duncanson In between Metallacyclopropane

Model two models Model

49
 Metallacyclopropane Model
In the metallacyclopropane extreme, the substituents on the
carbon are strongly folded back away from the metal and the
carbons rehybridize from sp2 to somewhat more closely to a sp3.
In this process, the metal gets oxidized and its formal oxidation
state increases by two units, the C-C bond lengths become more
of a single bond.

• The 2- Pt and Pd complexes of C60 come under this category.

50
• When the back bonding from the metal atom to the alkene ligand is
small, substituents on the alkene are bent only slightly away from the
metal and the C-C bond length is lengthened marginally from the free
alkene (Dewar-Chatt-Duncanson Model).

• With electron withdrawing substituents on the alkene, the back

donation is greater and substituents on the alkene are bent more
backwards and the C-C bond length approaches that of a single bond
(Metallacyclopropane Model).

M M
Dewar-Chatt cyclopropane

51
 Examples of complexes with alkenes having electron withdrawing groups

The electron withdrawing fluoro groups in F2C=CF2 as well as cyano groups of

(NC)2C=C(CN)2 make them better π-acceptor ligand. This effect weakens the C=C bond
but strengthens the alkene-metal bond.

52
Important Points

53
Effect on alkene stretching frequency ( νC=c)
Both σ donation and π back bonding weaken the C=C bond resulting in
the lower νC=c stretching frequencies compared to the free alkene in the
infrared spectra.

CH2=CH2 νC=c = 1623 cm-1

Fe(CO)4(CH2=CH2) νC=c = 1551 cm-1
Pd2Cl4(CH2=CH2) νC=c = 1525 cm-1
Pt2Cl4(CH2=CH2) νC=c = 1506 cm-1
CpRh(CH2=CH2)2 νC=c = 1493 cm-1

54
 Alkynes: Modes of Bonding to Metals
• Alkynes are essentially like alkenes, only with another perpendicular pair of -
electrons. Thus they can act as neutral 2 or 4 e- donors, depending on the needs
of the metal center. They are also much better bridging ligands because of this
second set of -electrons.
• Alkynes are better donors compared to alkenes and typically coordinate far more
readily to a metal for steric (more open, less hindered) and electronic (better donor,
2 or 4e- bonding) reasons.

C C C C

M M

R R R
R R R
C C C C
C C

M M M M M M
Possible modes of binding of alkynes to metal centers
55
Synthesis of metal – alkyne complexes
R
R
C
C
Co2(CO)8 + R-C C-R
(CO)3 Co Co (CO)3

But
Cl

But2C2, EtOH H2NR Pt

Na2[PtCl4]
4-MeC6H4-NH2
Cl
But

But

PPh3
Ph2C2, Pt
(Ph3P)2Pt(C2H4)
PPh3

But 56
Reactions of Metal Complexes of Alkenes and Alkynes
• With cobalt and palladium compounds alkynes dimerize to give cyclobutadienyl
compounds

Oxidative
coupling

Co(+1) Co(+3)

57
• The most interesting reactions of alkynes with transition metals is the
trimerization of alkynes by cobalt, nickel and palladium salts.
• Example: acetylene and substituted acetylenes trimerise to benzene or its
derivative in the presence of catalysts like CpCo(COD) or CpCo(C2H4)

• Trimerisation reactions also occur with a combination of alkyne and nitriles or

analogous compounds to yield pyridine derivatives.

58 58
 Problems
Q1. Reaction of two moles of CpNa with MCl2 gave an unstable compound A with molecular
formula C10H10M (M is a first row TM). On reacting A with excess of a hydrocarbon gas B along
with K gave a stable compound C with the empirical formula C9H13M. Reaction of C with excess
diphenylacetylene gave a highly stable compound D with the molecular formula C33H25M along
with evolution of the gas B. Write the structures of compounds A to D.
Ans:

Q2. Which of the following metal alkene complexes do you think will look more like a
metallacyclopropane? Explain your answer.
(a) (CH2=CH2)Ni(PPh3)2 (b) (CH2=CH2)Fe(CO)4
Ans: (a) (CH2=CH2)Ni(PPh3)2, since it has a more electron rich metal.
Q3. Arrange the following compounds in the increasing order of ethylene C-C bond lengths

Ans: B<A<C<D
59
Q4. Predict the product(s) in the following reactions.

Q5. To which of the following structures will trifluoroethylene (F2C=CHF) bind most and least strongly?

Ans: bind strongly least strongly (d0)

60
 Phosphines (PR3) : Neutral Spectator Ligands
• Spectator ligands are ligands which are present on the metal centre but do not
take part in a reaction.
• Their properties (mainly steric and electronic) alter the reactivity of the metal
centre.
• Phosphines are some of the most widely used spectator ligands.

Phosphines (PR3) are excellent soft donor ligands (which are large and
polarisable) with a variety of substituents which differ in steric and
electronic properties. Variation of three R groups can effect:
• Significant change in the steric size of the phosphine
• Change in the basicity and nucleophilicity of the phosphine
• generation of a large number of multidentate polyphosphines (bis-,
tris-, tetra-, penta-, and hexaphosphine ligands are all known) that
can adopt specific coordination geometries as well as
stereochemistry.

• Triphenylphosphine (PPh3) is the most widely used monodentate phosphine as it

is air and moisture stable.
• Almost all alkyl phosphines are fairly to highly air-sensitive, get oxidised to
phosphine oxide on exposure to air.
61
The electron-donating ability of a phosphine ligand was determined by reacting one equivalent
of the phosphine (monodentate) with Ni(CO)4 to make a Ni(CO)3(phosphine) complex.

PR3 CO (cm-1) PR3 CO (cm-1)

P(t-Bu)3 2056.1 PPh2(C6F5) 2074.8
PCy3 2056.4 P(O-i-Pr)3 2075.9
P(i-Pr)3 2059.2 P(OEt)3 2076.3
PEt3 2061.7 PPhH2 2077.0
PMe3 2064.1 P(OMe)3 2079.5
PBz3 2066.4 PPh(OPh)2 2079.8
P(o-Tol)3 2066.6 PPh2Cl 2080.7
PMePh2 2067.0 PH3 2083.2
P(m-Tol)3 2067.2 P(OPh)3 2085.3
PPh3 2068.9 P(C6F5)3 2090.9
P(p-C6H4-F)3 2071.3 PCl3 2097.0
PPh2H 2073.3 PF3 2110.8

62
 Basicity of Phosphines
• The pKa values are typically
used as a measure of σ
donor capability of a
phosphines

• Generally, phosphines are

less basic compared to
amines
pKa of NEt3 = 10.87
pKa of PEt3 = 8.69

• There are many examples

of reactions where a less
electron donating
phosphine is displaced by
more electron donating
phosphine.

Grubbs’ First
Generation
Catalyst
63
 Different types of Phosphines
Me
Me Me
Me Me Me PR2 PCy2
MeO OMe
Me P Me
Me P Bu R=Cy, t-Bu
Sterically hindered and electron rich tertiary phosphines

Biphosphines Chiral Phosphines 64

 Carbenes as Ligands (:CR2)
• Carbenes are species which are highly reactive and rarely stable in free state.
• There are two types of carbenes-singlet (↑↓) and triplet (↑↑) carbenes.
• Two types of metal carbenes : Fischer Carbene and Schrock Carbene.

Fischer Carbene Complexes

✓ Metal is in a low oxidation state (electron rich) and bonding of the carbene is similar
to that of CO.
✓ Metal stabilized by electron accepting ligands
✓ Carbene is more close to singlet carbene
✓ Carbon is electron deficient (stabilized by heteroatoms/phenyl groups)
✓ M=C bond is relatively weak and have low rotational barrier
Synthesis
O-Li+ OMe
LiR Me3O+BF4-
(CO)5W-CO (CO)5W C (CO)5W C W(+2) – d4
R R
Fischer Carbene

Cr(+2) – d4 Fe(+2) – d6
Pt(+4) – d6

Other Examples of Fischer Carbene Complexes 65

Schrock Carbene Complexes
✓ Metal is in a high oxidation state (electron
deficient and stabilized by electron
donating ligands)
✓ Carbene is more close to triplet carbene
✓ Carbon is electron rich (destabilized by
heteroatoms groups)
✓ M=C bond is relatively strong and have
large rotational barrier
Ta(+5)-d0 Ta(+5)- d0
Examples of Schrock Carbene
Complexes
In the Fischer Carbene, donation of
electrons from the carbon to the metal
dominates (with some amount of back
donation to the carbene carbon’s p
orbital) leaving the carbene carbon
atom with a slightly positive charge.
In the Schrock Carbene, two covalent
bonds are envisaged between the
metal and carbon, both of them
polarised towards the carbon, giving it
a slight negative charge.
Alternately, the schrock carbene can be
considered as a Fischer carbene with
very strong back donation.
66
 N-HETEROCYCLIC CARBENES (NHCs)

• Typically, normal carbenes are very reactive and

short lived molecules that cannot be isolated. But
NHCs are quite stable.
• NHCs are imidazolidine ligands with sterically
encumbering groups such as mesityl, isopropyl
and admantyl, etc
• They are attractive alternatives to tertiary
phosphine ligands. [Phosphines-high cost(chiral),
sensitive to oxidation, etc].

Advantages of NHC:
• They are stronger donor than phosphines.
• The stronger M-C bond of the NHC complexes
favours reaction kinetics which involves less of NHC
dissociation from the metal complex
• The presence of sterically hindered groups bound to N atoms facilitate reductive
elimination of the product from the metal during catalysis.
• Their activity can be modified by introducing electronically different substituents on
the nitrogen atoms in the ring.
67
N-HETEROCYCLIC CARBENES and Olefin Metathesis Catalysts

Grubbs first generation catalyst as well as second generation catalyst, have

properties intermediate between Fischer and Schrock type carbenes.
68
Unique reactions in organometallic chemistry

➢ Oxidative Addition

➢ Reductive Elimination

➢ Migratory Insertion

➢  - Hydrogen Elimination

69
 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 Often the first step of the mechanism
dn dn-2

• OX state of metal increases by 2 units H2 oxidative

H
Ph3P PPh3 addition H PPh3
• Coordination number increases by 2 units Rh Rh
Ph3P Cl Ph3P Cl
• 2 new anionic ligands are added to the metal Rh+1
PPh3
Rh+3

Wilkinson’s Catalyst

Requirements for oxidative addition

✓ availability of nonbonded 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.

70
 Examples of Oxidative addition : Cis or trans ?
Depending on the nature of the adding group (polar, nonpolar) as well as the type of
mechanism involved (concerted, SN2, free radical and ionic) one can get either cis
addition products, a mixture of cis and trans addition products or in few cases trans
addition products.

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

Heteronuclear systems (MeI) Cis or trans
VASKA’s Complex

Note:
• d0 metals cannot undergo oxidative additions So always electron count the starting
and final metal complexes to check out the overall electron-count, metal oxidation
state and d-electron count.
• Compounds with 18 electrons cannot undergo oxidative addition without the
expulsion of a ligand.
e.g Ru(CO)4(PMe3) + MeI gives Ru(CH3)(I)(CO)3(PMe3) + CO
71
 Intramolecular Oxidative Addition: C-H Activation and
cyclo/ortho metallation

Agostic interaction

Oxidative Coupling

Ph2 Cl
Ph2 Cl
P
P H3C N Cr
H3C N Cr
P
P Ph2 Cl
Ph2 Cl
Cr(+5) d1
Cr(+3) d3
13e-
15e-

72
 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

Final step in many catalytic cycles 73

 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
74
 Types of Migratory Insertion
X X
X = Anionic
M A B M A 1, 1 - migratory insertion
ligand = H, R,
B Ar, COR
X
X
A AB = Neutral
B 1, 2 - migratory insertion ligand = CO,
M
M A alkene, alkyne
B

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
75
 Migration versus Insertion

A migration occurs when

the anionic ligand moves
and performs a
nucleophilic-like
intramolecular attack on
the electrophilic neutral
legand.

An insertion occurs when

the neutral ligand moves
and gets inserted into the
bond between the metal
and the anionic ligand.

Most systems studies have been shown to undergo migration and not insertions.

76
 -Hydride elimination
Beta-hydride elimination is a reaction in which an alkyl group having a  hydrogen,  bonded
to a metal centre is converted into the corresponding metal-bonded hydride and a  bonded
alkene. The alkyl must have hydrogens on the beta carbon. For instance butyl groups can
undergo this reaction but methyl groups cannot. The metal complex must have an empty (or
vacant) site cis to the alkyl group for this reaction to occur.

No change in the formal oxidation state of the metal

mechanism H H H H H
H H H
C H C C
M
M C M C C
H H H H H H

Can either be a vital step in a reaction or an unwanted side reaction

77
 -hydrogen elimination does not happen when
• the alkyl has no -hydrogen (as in PhCH2, Me3CCH2, Me3SiCH2)
• the -hydrogen on the alkyl is unable to approach the metal (as in C≡CH)
• the M–C–C–H unit cannot become coplanar

Question: Select the most unstable platinum  complex from the given list. Justify
your answer

H
Ph3P C Ph3P Ph3P
SiMe3 Et3P C
Pt Pt Pt Pt
Ph3P SiMe3 Ph3P Ph3P
Et3P C
C
H
A B C D

No  -H  -H unable to MCCH unit will not be

approach M coplanar

78
 Problem solving
Classify the following reactions as oxidative addition,
reductive elimination, (1,1 / 1,2)migratory insertion, - H
elimination, ligand coordination change or simple addition

(a) [RhI3(CO)2CH3]− → {RhI3(CO)( solvent)[C(O)CH3]}−

(b) Ir(PPh2Me)2(CO)Cl + CF3I → Ir(I)(CF3)(PPh2Me)2(CO)Cl

(c) TiCl4 +2 Et3N → TiCl4 (NEt3)2

(d) HCo(CO)3(CH2=CHCH3) + CO → CH3CH2CH2Co(CO)4

Step 1. determine the oxidation state of the metal in reactant and product
Step 2. count the electrons for reactant and product
Step 3. see if any ligand in the reactant has undergone change

Answer: (a) 1,1- Migratory insertion; (b) Oxidative addition; (c) Simple addition;
(d) 1,2- Migratory insertion 79
Question:

Answer: (a)
80
 Problem solving- fill in the blanks

Oxidative addition 1,2 Migr. Insertion

1,1 Migr. Insertion

81
 Catalysis using organometallic Catalysts
A catalyst typically increases the reaction rates by lowering the activation energy by opening
up pathways with lower Gibbs free energies of activation (G).

Gibbs energy of activation

• A catalyst does not affect the Gibbs free
energy of the overall reaction because G
is a state function (G depends only on the
uncatalyzed current state of the system and not on
the path that leads to the state).
• Thus, reactions which are
Gibbs Energy

catalyzed
thermodynamically unfavourable cannot
be made favourable by a catalyst.
• Catalyst product complex should not be
too stable, i.e, Product should not bound
to the catalyst too strongly.
• Catalyst Poisoning: If reactants or
products make stable intermediate with
catalysts.
stable intermediate

Reactants Products
82
 Homogeneous versus Heterogeneous Catalysis
Catalysts are classified as homogeneous if they are soluble in the reaction medium (catalyst
and reactants in the same phase) and heterogeneous if they are insoluble.

Parameter Heterogeneous Homogeneous

Phase
Required temperature
Catalyst Activity
Product selectivity
Catalyst recycling
Gas/solid Usually liquid/ or solid
soluble in the reactants
High Low ( less than 250°C)
Low High
Less (often mixtures) More
Simple and cost effective Expensive and complex

Reaction mechanism Poorly understood Reasonably well understood

Product separation Easy Elaborate and sometimes
from catalyst problematic
Fine tuning of catalyst Difficult Easy

83
Comparing different catalysts; Catalyst life and Catalyst efficiency

Turnover Number (TON)

• The absolute number of passes through the catalytic cycle before the catalyst
become deactivated is called the 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 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

84
 Catalytic Hydrogenation of Alkenes
• Although the reaction of hydrogen gas with ethylene is thermodynamically
favorable, [G0 = -101 kj/mol.], it does not take place at room temperature
and pressure.

• Many heterogeneous catalysts were found to bring about hydrogenation of

alkenes/alkynes but the first example of an effective and rapid
homogeneous catalyst, active at room temp and atm pressure was
WILKINSON’S CATALYST, (PPh3)3RhCl.
Sir Geoffrey Wilkinson

Synthesis:

• Square planar complex

• 16 electron complex
• Rh(+1)

85
 Conventional Catalytic cycle for hydrogenation with
Wilkinson’s catalyst
P P
Rh 16 e
P Cl
P P

P
The first step of this catalytic
reductive Cl Rh H2 oxidative cycle is the cleavage of a PPh3
elimination 14e P addition to generate the active form of
the catalyst followed by
RCH2CH3 oxidative addition of
dihydrogen.
R H H
CH2
P P
H2C Rh H Rh 16 e
P P
16 e Cl Cl

• If PPh3 is replaced by PEt3,

R there is no catalytic activity.
1, 2 -migratory alkene
insertion
P coordination
H H
Rh P = PPh3
P Cl

R
18 e
NOTE: Ethylene can’t be used because ethylene-Rh complex is very stable (Catalyst poisoning)
86
 Relative reactivity of alkenes for homogenous catalytic hydrogenation

R R R R
> > > >
R
R R R R
> >
R R R R
R

Relative reactivity of alkenes for hydrogenation using Wilkinson’s Catalyst

✓ Terminal alkynes are hydrogenated more rapidly than terminal alkynes,

✓ Conjugated dienes are reduced more slowly than isolated alkenes,
✓ Internal and branched alkenes/alkynes undergo hydrogenation more slowly than
terminal ones, and
✓ Substrate containing polar functional groups are hydrogenated more rapidly than
those having no such groups, because polar functional group assist the coordination
better with the catalyst.
87
Unlike heterogeneous hydrogenation catalysts, homogeneous catalysts
provide high site selectivity in hydrogenation.

O
cis- disubstituted Pd/C
O
acetone, H2(1atm), rt
O
O heterogeneous catalysts 75%
O
O

O
Wilkinson's catalyst
tetrasubstituted
benzene, H2 (1 atm), rt O
O
homogeneous catalysts 95%

Cis versus trans disusbstituted olefins: cis preferentially hydrogenated

O
cis O
COOMe
Wilkinson's catalyst
COOMe

H2, C6H6, acetone

HO trans
HO
OAc
OAc
88
 Hydroformylation Reaction
Hydroformylation is used to describe the addition of a H2 and CO to an olefinic
double bond with the formation of aldehydes containing one more carbon atom
than the olefin.

(n) (iso)

• It is the largest homogeneous catalytic process worldwide.

• 7 X 106 tons/year of aldehydes. (Further to reduced to alcohols)

Why hydrogenation is not taking place? (Explanation from thermodynamics)

• Alkane is thermodynamically
favoured product and not the
aldehyde.
• Since, aldehyde is the major
product, it shows that the
reaction is kinetically controlled.

89
 Four catalytic processes for hydroformylation.

✓ The Co2(CO)8 catalyzed process

✓ The Co2(CO)8/PR3 catalyzed process
✓ The HRh(CO)(PPh3)3 catalyzed process
✓ The biphasic HRh(CO)(PR3)3 process (R = m-C6H4SO3Na)

(n) (iso)

The major differences between these process are

(a) in the operating temperatures and pressures
(b) the ratio of n- aldehyde to iso aldehyde obtained as product (n/iso ratio)
(c) the rate of the reaction and the control of side reactions such as
hydrogenation
(d) ease of recovery of catalyst
90
 Co2(CO)8 catalyzed hydroformylation process

d(aldehyde)/dt = k[alkene][Co][pH2][pCO]-1

The inverse dependence on the concentration of CO agrees with the

mechanistic requirement of CO dissociation from 18 electron species
such as HCo(CO)4. However if the CO partial pressure is not kept high
enough, metallic cobalt gets deposited due to the thermal instability of
HCo(CO)4. Increasing the CO partial pressure decreases the
hydroformylation reaction rate and reduces the extent of alkene
isomerization reaction. Therefore a balance is required.
Partial pressure of CO = 200-300 bar
Temp = 110-160 °C
91
Catalytic cycle for Hydroformylation using HCo(CO)4
Co2(CO)8
H2
HCo(CO)4 18 e-

CO
RCH2CH2CHO HCo(CO)3 CH2=CHR
Alkene coordination
Reductive
16 e-
Elimination

RCH2CH2CO- Co(H2)(CO)3 HCo(CO)3(CH2=CHR)

18 e- 18 e-
1,2 migratory
Hydroformylation insertion
with Co2(CO)8
H2

RCH2CH2Co(CO)3
RCH2CH2CO-Co(CO)3
16 e-
16 e-
CO
Carbonyl
Migratory
Insertion RCH2CH2Co(CO)4
1,1-MI
18 e-
92
 Phosphine modified Cobalt Catalysts- Co2(CO)8/PR3

Unstable Stable
Therefore we need PPh3 being good sigma donor
high pressure will increase back bonding to Co and stability of
Catalyst will increase

Addition of trialkyl phosphine ligands to cobalt carbonyl

catalyst brought about a dramatic change is the rate of the
reaction and selectivity. The electron donating PR3 when
substitutes a CO, brings about more back bonding of the
rest of the CO to the metal thereby increasing the thermal
stability of the catalyst against decomposition. This brings
down considerably the CO partial pressure required to
stabilize the catalyst from 200-300 to 50-100 bars.
93
 Rhodium-Phosphine Catalysts- HRh(CO)(PPh3)3

d(aldehyde)/dt = k[alkene][Rh][pH2]

• In this case there is no dependent on partial pressure of CO. So this system works
at pressure of 15-25 bar.

• As halides were found to be inhibhitors for hydroformylation, the original

Wilkinson’s catalyst was modified to contain no halides. HRh(CO)(PPh3)3

• The main drawback of the Rhodium- PPh3 catalyst was due to a practical problem
that at high temperatures required for product separation of long chain
aldehydes, the catalyst decomposes. So the application was limited to C3 and C4
alkenes.
• This problem was solved by using a water soluble phosphine in the catalyst and by
resorting to biphasic catalysis. HRh(CO)(PR3)3 ( R = m-C6H4SO3Na)

94
Catalytic Cycle for hydroformylation using Rhodium Catalyst
H
CO
Ph3P Rh
PPh3 18 e-
PPh3

-PPh3

Ph3P H CH2=CHR
RCH2CH2CHO Rh Alkene coordination
Reductive OC PPh3
Elimination
16 e-
H
H R
Ph3P H
Ph3P
18 e- Rh
O
Rh 18 e-
OC Ph3P
C
PPh3 CO
CH2CH2R

Hydroformylation 1,2 migratory

with HRh(CO)(PPh3)3 insertion

H2
O

Ph3P CCH2CH2R Ph3P CH2CH2R

Rh Rh
16 e- OC PPh3 OC PPh3 16 e-

CO
Carbonyl
Migratory CH2CH2R CO
Ph3P
Insertion Rh
OC PPh3
95
18 e-
Comparison of different hydroformylation Catalysts

96
 Olefin Metathesis

Grubbs Schrock
➢ Occurs in the presence of carbene complexes- GRUBBS catalysts and
SCHROCK Catalysts.
➢ Robert H. Grubbs, Richard R. Schrock and Yves Chauvin : Nobel Prize - 2005.
PCy3
Cl N N N N
Ru Cl
Cl
Cl Ru Ru
PCy3 Cl Cl
PCy3 O

Grubb's first-generation
catalyst Grubb's second-generation Hoveyda-Grubb's
catalyst Catalyst
97
 Mechanism:

R'' R'' R''

LnM C MLn
MLn

C C
R R' R R'
R R'
Metallacyclobutane

• The commonly accepted mechanism for the olefin metathesis reaction was
proposed by Chauvin and involves a [2+2] cycloaddition reaction between a
transition metal alkylidene complex and the olefin to form an intermediate
metallacyclobutane. This metallacycle then breaks up in the opposite fashion
to afford a new alkylidene and new olefin. If this process is repeated enough,
eventually an equilibrium mixture of olefins will be obtained.

• Cycloaddition reactions between two alkenes to give cyclobutanes is symmetry

forbidden and occurs only photochemically. However, the presence of d-
orbitals on the metal carbene fragment breaks this symmetry and the reaction
is quite facile.

98
 CHR

RCH=CHR

CH2

99
 L
Cl R L = PCy3 (Grubbs first generation catalyst)
Ru
Cl = NHC (Grubbs second generation catalyst)
16e
PCy3

-PCy3

L
Cl R
Ru R'
Cl
R
14 e-
(R = R’ after first
cycle)

L
L R
Cl
Cl
Ru
R Cl Ru
Cl

R' R'
L
Cl R
Ru
Cl

R'

Formation of the metallacycle in the mechanism of olefin metathesis

100
Different types of olefin metathesis reactions

1,3-diene product 101

DECARBONYLATION WITH WILKINSON’S
CATALYST

Diphenylphosphoryl Azide (DPPA) 102