Organometallic Chemistry

Raja Angamuthu
Department of Chemistry
Indian Institute of Technology Kanpur
Ø 7 Steps in Mastering Organometallics

ü Periodic Table
ü Ligands
ü Electron Count (18e rule)
ü Oxidative Addition
ü Reductive Elimination
ü b-Hydride Transfer/Elimination
ü Migratory Insertion
Ø Periodic Table

Sc Ti V Cr Mn Fe Co Ni Cu Zn

Y Zr Nb Mo Tc Ru Rh Pd Ag Cd

La Hf Ta W Re Os Ir Pt Au Hg

Early Middle Late

Ø Periodic Table

d1 d2 d3 d4 d5 d6 d7 d8 d9 d10
Sc2+ Ti2+ V2+ Cr2+ Mn2+ Fe2+ Co2+ Ni2+ Cu2+ Zn2+

Y2+ Zr2+ Nb2+ Mo2+ Tc2+ Ru2+ Rh2+ Pd2+ Ag2+ Cd2+

La2+ Hf2+ Ta2+ W2+ Re2+ Os2+ Ir2+ Pt2+ Au2+ Hg2+
Ø Ligands

ü Nature of the ligands

ü Charge of the ligands

ü Binding modes

ü Number of electrons donated

Ø Dihydrogen: Neutral 2e donor

R3
P O
C
H Curious to know?
H Ø IR
OC W
Ø NMR
M H Ø X-ray Diffraction
H OC P Ø Neutron Diffraction
R3

W(η2-H2)(CO)3[P(i-Pr)3]2

J. Am. Chem. Soc. 1984, 106, 2, 451–452; J. Chem. Educ. 1996, 73, 10, 988
Ø Hydride: Anionic 2e donor

H
Ph 3P
Rh PPh 3
Ph 3P S S
C Fe Fe
O Cp* Cp*
H

Curious to know?
Ø What is Cp*

J. Chem. Soc. A, 1968, 3133-3142; Inorg. Chem. 2015, 54, 21, 10243–10249
Ø Hydride: Anionic 2e donor
P
R R 2+

H R P P R
H
R R
P H P Cu Cu
R P H P R
P H
P Cu
H H P P
R R R R

P
[(R3P)Cu(μ3-H)]6 [Cu3(dcpm)3(μ3-H)]2+
Stryker’s reagent

J. Am. Chem. Soc. 1989, 111, 3472–3473; J. Am. Chem. Soc. 2005, 127, 4562–4563
Ø Hydride: Anionic 2e donor

Ru Co

Ru Co
Ru H Ru Co H Co
Ru Co

Ru Co
[HRu6(CO)18]− [HCo6(CO)15]−

J. Chem. Soc., Chem. Commun., 1976, 945-946; Angew. Chem. Int. Ed. 1998, 37, 2193–2197
Ø Halides: anionic 2e, 4e or 6e donor

PPh 3

Ph 3P I Cu
Ph 3P
Cu I
Cu I

I Cu

PPh 3

J. Am. Chem. Soc. 76, 4281–4284; Inorg. Synth., 21, 74–78; Dalton Trans., 2019,48, 7899-7909
Ø H2O, ROH, RSH, R2O, R2S:
H H H H
O S

M M

R
R H R H
O S
S
R M
M M
M
Cl CO
S S Cl
Ru Ru
R R R R Cl S
S
O S CO Cl

M M
Neutral 2e and 4e donors
Neutral 2e donors Dalton Trans., 2010, 39, 5713–5720
Ø HO – and HS :
–

PCy 3 H
OC H CO CO H
Ru Ru Cy3P OC
H O PCy 3
(tBu) 2P Ni P(tBu) 2 PCy 3 Cl Ru Ru PCy 3
H
H
OH O H
2e donor 4e donor O
OC
Cl H
H Ru Ru
SH Cp* S Rh H O
Ti CO PCy 3
SH Rh S Cp* Cy3P H
H 6e donor
Cl
2e donor 4e donor Curious to know about (µ3-SH) ???
Chem. Eur. J. 2012, 18, 6915 – 6927; Organometallics 1985, 4, 524-528;
Organometallics 2006, 25, 1047–1051; Organometallics 1997, 16, 151–154
Ø RO – and RS :
–
P(tBu) 2
O S
O
Pd OCH3 Ti Ti
O
Fe(CO) 3
(OC) 3Fe
P(tBu) 2
Fe(CO) 3
2e donor 4e donor 6e donor H
R
(OC) 3Mn S
R
S S Mn(CO) 3
Ti R S Mn(CO) 3
S S S
Fe Fe (OC) 3Mn S
Cp* Cp*
H R
2e donor 4e donor Curious to know about (µ3-OR) ???

J. Am. Chem. Soc. 2011, 133, 17713–17726; Inorg. Chem. 2017, 56, 3324−3334; Inorg. Chem. 2015, 54, 21,
10243–10249; Inorg. Chim. Acta 2018, 480, 47–53; Dalton Trans., 2016, 45, 13222-13233
Ø O2 and S2
2– 2–:

O O +

Ru S
Ni N CO
Cp* S OC CO
N Ir

4e donor O
OC C CO S S
Ir Ir CO
+ OC Fe Fe
S S O Cp* Cp*
O
S S
O Ir O
Ru S OC CO
Ni N
Cp* S
N

4e donor 4e donor 4e donor

Organometallics 2003, 22, 8, 1619–1625; Inorg. Chem. 2019, 58, 21, 14338–14348;
Dalton Trans., 2017,46, 3820-3824
Ø O 2– and S :
2–

P(tBu) 2 +

O Ph
N tBu
Pt O O N tBu
Ti Re
S tBu N O
Ph tBu
N
Me 2

4e donor 4e donor 6e donor

Nature 2008, 455, 1093–1096; Organometallics 1999, 18, 5502–5510; Inorg. Chem. 2011, 50, 20, 9864–9878
Ø O 2– and S :
2–

4e donor

8e donor 6e donor

6e donor
Inorg. Chem. 2009, 48, 8154–8163; Dalton Trans., 2011,40, 4212-4216; Angew. Chem. Int. Ed. 1991, 30, 1126–1127
Ø R3N, R3P, R2 N:
–
P(tBu) 2
2e 2e
(Me 3Si)2N Fe N(SiMe 3)2 M N
Ir NH 3 R
Fe Fe R
Fe
P(tBu) 2 (Me 3Si)2N N(SiMe 3)2
2e donor
2e 2e pyramidal
2e donor

N
Ph 2
Ru PPh 3 Ru P N
P Mo P
Ph 3P Cl Cl P N Ni N
Ph 2 ON CO

2e donor 4e donor 2e donor; planar !!

Science 2005, 307, 1080-1082; Organometallics 2009, 28, 7006–7014; Angew.Chem. Int.Ed. 2017, 56,3585 –3589;
Chem. Asian J. 2014, 9, 328 – 337; J. Am. Chem. Soc. 2008, 130, 26, 8156–8157;
Ø R2 N– and R2 P:
–

R 2N NR 2
P
Ti
Fe P Ru
PPh 3
Fe H H Fe Cy2P
2e donor 4e donor CO
R 2N H Fe H NR 2

Fe H H Fe

Fe
P P Ru PPh 3
R 2N NR 2
(OC) 3Fe Fe(CO) 3 Cy2P CO

4e donor 4e donor 2e donor

Angew.Chem. Int. Ed. 2017, 56,3585 –3589; Organometallics 1983, 2, 8, 1049–1051;
J. Am. Chem. Soc. 1977, 99, 7381–7383; Organometallics 2007, 26, 1473-1482
Ø RN :
2–
H
F 3C
Cl Cp*Ir N
iPr Cp
PiPr 2 M N
Ti N CF3 H
R N IrCp*
N iPr H N IrCp*
N Ti 4e
CH2tBu CF3 N Ti Cp*Ir N
Cp H
PiPr 2 Cl
CF3
M N R
4e donor 4e donor 6e donor
6e
Cp*

R R R
Ti
HN NH N N N
N
Mo M N Ar M M M M M M
Ti Ti
Cl N 4e Cp* N Cp*
Cl tBu H 4e 4e 6e
6e donor 4e donor
Organometallics 2005, 24, 7, 1390–1393; Inorg. Chem. 1996, 35, 1773-1777; Chem. Commun., 2011,47, 5620-5622;
Inorg. Chem. 2020, 59, 11, 7631–7643; J. Am. Chem. Soc. 2011, 133, 8880–8883
Ø N ,
3– P :
3–

Ar N R R
N R
N
Re
Fe Fe R
N N
Ar R P
R R
R R
Fe
OC CO
6e donor 6e donor Co Co CO
N OC
OC CO
R N R
P Cl Fe Fe Co
iPr iPr R R OC CO
R R
iPr P Mo P iPr R CO
P
Fe Fe R R
P
R
R R

6e donor 6e donor 6e donor 6e donor

Inorg. Chem. 2019, 58, 13492−13501; Chem. Sci., 2017,8, 4108-4122;

Angew.Chem. Int. Ed. 2001, 40,2859 –2861; J. Organomet. Chem. 1976, 111, 61-64
Ø N :
3–

Fe(CO) 3 Fe(CO) 2 3
O
C

(OC) 2Fe Fe(CO) 3 (OC) 2Fe Fe(CO) 2

(OC) 3Fe N Fe(CO) 3
O C N C O O C N C O

(OC) 3Fe Fe(CO) 3 (OC) 2Fe Fe(CO) 2 (OC) 2Fe Fe(CO) 2

C
C
O Fe(CO) 2 O

Chem. Sci., 2016,7, 2728-2735

 Common Organic Ligands
H
H
H

H H
H H

H
H H
H H

Carbon Monoxide (CO) is also an important ligand

 Terminology: Hapticity
h x
“eta-x” was originally developed to indicate how many contiguous donor atoms of a
p-system were coordinated to a metal center. Hapticity is another word used to describe the
bonding mode of a ligand to a metal center. An h5-cyclopentadienyl ligand, for example, has
all five carbons of the ring bonding to the transition metal center.
hx values for all-carbon based ligands where the x value is odd usually
indicate anionic carbon ligands (e.g., h5-Cp, h1-CH3, h1-allyl or h3-allyl, h1-
CH=CH2). The # of electrons donated (ionic method of electron counting) by the
ligand is usually equal to x + 1. Even hx values usually indicate neutral carbon p-
system ligands (e.g., h6-C6H6, h2-CH2=CH2, h4-butadiene, h4-cyclooctadiene).
The # of electrons donated by the ligand in the even (neutral) case is usually just
equal to x.
 Common Ligands and Electrons Contributed
q Electron Counting

a) Common organometallic ligands

are assigned an electron count
and charge; those that are
commonly ions are treated as
such

b) The overall charge on the complex

must equal the total charge on
ligands plus the charge on the
metal; this helps determine d-
electron count of metal

c) Add up all electrons from metal d

orbitals and ligands to find total e-
count
 Varying Hapticity = Varying Electron Contribution
q Consider the cyclopentadienyl anion.

q How do we get the cyclopentadienyl anion? How to understand its structure?

Varying Hapticity = Varying Electron Contribution

2 electron donor

4 electron donor

6 electron donor
The allyl anion has similar attributes

A molecule can have the

Same ligand in different
hapticities.

4 electron donor 2 electron donor

Dewar-Chatt-Duncanson Model for Metal-Alkene Bonding

s-component: p-component:
C-C p → empty metal orbital occupied metal d → empty C-C p*

Note the similarity to CO ligands...

s-component: donation of C lone pair

p-component: backbonding into CO p*

3I3-7
 Metal-Carbonyl Complexes
q The carbonyl ligand forms a huge number of complexes with metal ions,
most commonly in low oxidation states, where it binds to the metal
through its C-donor, as in the complexes below, where all the metal ions
are zero-valent:

[Ni(CO)4] [Fe(CO)5] [Cr(CO)6]

 Metal-Carbonyl Complexes: 18 Electron Rule
q Why in the above complexes Ni(0) has four C≡O groups attached to it,
Fe(0) five C≡O, and Cr(0) six C≡O?

q The eighteen electron rule allows us to explain this observation.

q The charge on the complexes is zero. Since CO is a neutral molecule, the

metals are in the zero oxidation state.

[Ni(CO)4] [Fe(CO)5] [Cr(CO)6]

Ni(0) = d10 Fe(0) = d8 Cr(0) = d6

4 x CO = 8 5 x CO =10 6 x CO = 12
18 e 18e 18e
 Example: A Simple Case

CH3 1) There is no overall charge on the complex

2) There is one anionic ligand (CH3-, methyl
R3P CO group)
Re 3) The Re metal atom must have a +1 charge to
compensate for the one negatively charged
PR3 ligand. So the Re is the in the +1 oxidation
CO state. We denote this three different ways:
Re(+1), Re(I), or ReI.

Re(+1) d6
2 PR3 4e-
2 CO 4e-
CH3- 2e-
CH2=CH2 2e-
Total: 18e-
Example: Simple Case with Somewhat Unusual Ligand

1) There is a +2 charge on the

CNCH3 2+ complex
H3CNC
CNCH3 2) The CNCH3 (methyl isocyanide)
H3CNC Mo ligand is neutral, but lets check the
Lewis Dot structure to make sure
H3CNC CNCH3 that is correct:
CNCH3
C NCH3
3) Because there is a +2 charge on the
complex and all neutral ligands
Mo(+2) d4 present, the Mo has a +2 charge &
oxidation state.
7 CNCH3 14e-
Total: 18e-
 Example: Somewhat Tricky!
Me 1) There is no overall charge on the complex
2) There is one anionic ligand (C3H5-, allyl)

Rh
3) The top ligand is NOT a MeCp-!
PPh3 It is a neutral diene that has a H
attached to the methyl-
substituted ring carbon. This is
a neutral 4e- donor.

4) Because the complex is neutral and there is one Rh(+1) d8

anionic ligand present, the Rh atom must have a +1 PR3 2e-
charge to compensate for the one negatively
charged ligand. So the Rh atom is in the +1 h4-C5H5Me 4e-
oxidation state. h3-C3H5- 4e-
Total: 18e-
 18 Electron Rule Explains Some Observations
q The compound Mn2(CO)10 exists but Mn(CO)5 does not.
q A species such as [Mn(CO)5] would have only 17 e.
q Each Mn contributes one electron to the valence shell of the other Mn,
giving the metal-metal bonded species [(CO)5Mn-Mn(CO)5]. To check on
the 18e rule, we look at one metal at a time:

Mn-Mn Mn(0) = d7
bond 5 C≡O = 10
Mn Mn-Mn = 1
Mn

18 e
[Mn2(CO)10]
 Bridging Carbonyl Ligands
bridging
carbonyls
q Carbonyls may form bridges between
two metals, where they donate one
electron to each metal in working out
Co Co the 18 electron rule.
q In [Co2(CO)8] , each Co has three
terminal CO’s, two bridging CO’s, and a
Co-Co bond:

Co-Co
bond Co(0) = d9
[Co2(CO)8] 3 CO’s = 6
2 bridge CO’s = 2
Co-Co bond = 1
18 e
 Terminolgy for Bridging Ligands
µx “mu-x” is the nomenclature used to indicate the presence of a
bridging ligand between two or more metal centers. The x refers to the
number of metal centers being bridged by the ligand. Usually most authors
omit x = 2 and just use µ to indicate that the ligand is bridging the simplest
case of two metals.

(CO)3Co(μ-CO)2Co(CO)3
[1]

[1]+

[1]2+
[1]

[1]+

[1]2+
O
 P P
CH3
H 3C
CH3
Tolman’s Cone Angle and Electronic Parameter
The electron-donating ability of a phosphine ligand was determined by
measuring the nCO of a Ni(CO)3(PR3) complex:

Lowest CO stretching O
frequency: C
most donating OC Highest CO stretching
frequency:
phosphine R least donating
phosphine
C
O (best p-acceptor)

The size or steric bulk of a

phosphine ligand was
determined from simple 3-D
space-filling models of the
phosphine ligand
coordinated to a Ni atom: cone angle q
M
 OXIDATIVE ADDITION
REDUCTIVE ELIMINATION
 Types of Substrates (X-Y)
q Depending on the nature of the substrate (X-Y), the mechanism of the
oxidative addition may differ .
q There are three main classes of molecules (substrates) that can perform
oxidative additions to metal centers:
Ø Non-Electrophillic; Non-Electrophillic “Intact”; Electrophillic
Non-electrophillic: These molecules do NOT contain electronegative atoms
and/or are not good oxidizing agents. These molecules usually require the
presence of an empty orbital on the metal in order for them to pre-coordinate
prior to being activated for the oxidative addition rxn.
Non Electrophilic Substrates that Do Not Fragment
Non-electrophillic “Intact”: These molecules have a double or triple bond
present. One also needs a metal center with an empty orbital (16e- or lower
count) in order to pre-coordinate the ligand before the oxidative addition occurs.

q Alkenes and alkynes are typical “intact” ligands that can perform an oxidative
addition without fragmenting apart.

metallocyclopropene
R
R R PMe3
PMe3
Me3P Pt Pt
PMe3
-PMe3 PMe3
R
 Electrophilic Substrates

Electrophillic: These molecules do contain electronegative atoms and are good

oxidizing agents. They are often considered to be “reactive” substrates.
Examples: X2 (X = Cl, Br, I), R-X, Ar-X, H-X, O2, etc.
 Oxidative Addition: Electrophilic Substrates
q In the case of a starting 18e- complex (shown below) only one of the two
anionic ligands (usually the strongest binding) generated from the oxidative
addition will end up coordinated to the metal unless a separate substitution
reaction occurs.
Reductive Elimination: Effect of Ligand Dissociation
q Sometimes, more than one reductive elimination possibilities arise from
saturated 18e- complexes (so long as the two ligands that you want to
reductively eliminate are cisoidal to one another).

q An understanding of the electronic requirements can facilitate reaction

engineering to favour one option over the other.

Both pathways occurred; reaction was slow (~ many hours)

Reductive Elimination: Effect of Ligand Dissociation
q It has been shown that reductive elimination can be promoted by a ligand
dissociation generating an unsaturated and more electron-deficient metal
center.
 Migratory Insertion
q A migratory insertion reaction is when a cisoidal anionic and neutral ligand
on a metal complex couple together to generate a new coordinated anionic
ligand. This new anionic ligand is composed of the original neutral and
anionic ligands now bonded to one another.

q There is NO change in the oxidation state or d electron-count of the metal

center.
 Migratory Insertion: Who Migrates to Whom?
Migration

O O CH3
C a MIGRATION rxn involves the
OC CO OC CO anionic ligand doing a
Mn Mn nucleophillic-like attack on the
OC CH3 OC neutral ligand. This involves the
C C anionic ligand moving to the site
O O where the neutral ligand is
coordinated. An empty
Mn(+1) Mn(+1) coordination site is left behind.
18e- 16e-
Insertion
O
C an INSERTION rxn involves the
OC CO OC CO neutral ligand moving over to
Mn Mn O where the anionic ligand is
OC CH3 OC coordinated and "inserting" into
C C the anionic ligand-metal bond to
CH3 generate the new anionic
O O
ligand. An empty coordination
Mn(+1) Mn(+1) site is left behind from where
18e- 16e- the neutral ligand originally was
located.
 Who Migrates to Whom? Experiment Design
q Four products of insertion are
possible, corresponding to
reaction of the four CO
ligands cis to the methyl
ligand. Consider both CO
migration and Me migration
as possible at this point.

q Product D is impossible if we only allow the Me group to migrate—the

spot trans to the labelled CO is another CO ligand, so that spot can only pick
up L if CO migrates (not if Me migrates).

q On the other hand, product C must have come from the migration of Me,
since the Me group has moved from a cis to a transposition relative to the
labeled CO in product C.

q Products A, B, and C were observed, but not D, supporting a mechanism

involving Me migration. Other experiments since support the idea that
most of the time, the alkyl group migrates onto CO.
 Migratory Insertion of Alkenes

q Successive migratory insertions can lead to chain elongation

 Eliminations
q The most common elimination is b-hydride elimination. It can be thought of
as the opposite of migratory insertion.

q No change in formal oxidation state

q You must have an empty orbital that is cisoidal to the group that you are
doing an elimination reaction on. Alternatively, a cisoidal labile ligand that
can easily dissociate to open up an empty orbital.
 Catalytic Applications of Organometallic Complexes
Catalyzed rxn
proceeding through
an intermediate

Ea

Ea
q 1850 Berzelius DG catalyzed

q 1895 Ostwald: a catalyst is a substance Reactants

DG
that changes the rate of a chemical reaction
Products
without itself appearing into the products.

Reaction Coordinate
A catalyst
q Speeds up a reaction Alters the rate of the reaction
q Enables a reaction to proceed that otherwise does not without it
q Typically added in non-stoichiometric amounts
q Remains unchanged at the end of the reaction

Catalysis is a kinetic phenomenon.

 Homogeneous And Heterogeneous Catalysis

q Homogeneous catalysis: Catalyst and reactants are in the same phase.

q Heterogeneous catalysis: Catalyst and reactants are in the different phase

(the catalyst is usually insoluble; reaction occurs on its surface).
 Homogeneous And Heterogeneous Catalysis
q Most catalytic reactions in industry use heterogeneous catalysis

Homogeneous catalysts:
Advantages generally far more selective for a single product
far more active
far more easily studied from chemical & mechanistic aspects
far more easily modified for optimizing selectivity
Disadvantages far more sensitive to permanent deactivation
far more difficult for achieving product/catalyst separations
 Terminologies in Catalysis
Turnover (TO) -- One loop through the catalyst cycle. Typically one equivalent of
reactant is converted to one equivalent of product (per equivalent of catalyst).

Turnover Frequency (TOF) or Turnover Rate -- The number of passes through the
catalytic cycle per unit time (typically sec, min or hrs). This number is usually
determined by taking the # of moles of product produced, dividing that by the #
of moles of catalyst used in the reaction, then dividing that by the time to
produce the given amount of product.
Example: If 1 mole of catalyst converts 1000 moles of CO→CO2 in 10 seconds
then TOF = (1000/(1*10 s) = 100 s-1

Turnover Number (TON) -- The absolute number of passes through the catalytic
cycle before the catalyst becomes deactivated. A large TON (e.g., 106 - 1010)
indicates a stable, very long-lived catalyst. TON is defined as the amount of
reactant (moles) divided by the amount of catalyst (moles) times the % yield of
product.
Example: If 1 mole of catalyst converts 1000 moles of CO→CO2 (100% yield) then
TON = 1000
 Important Catalytic Reactions: Alkene
Hydrogenation
q Alkene + H2 ® Alkane
q Catalyst required, usually Pt, Pd, or Ni.
q Finely divided metal, heterogeneous

q Syn addition
Homogeneous Catalytic Processes
 Hydrogenation of Alkenes

The most commonly used catalyst is the Wilkinson’s Catalyst

Many alkenes are hydrogenated with hydrogen at 1atm pressure or less.

Wilkinson’s catalyst is highly sensitive to the nature of the phosphine ligand and the
alkene substrate.
Analogous catalysts with alkyl phosphine ligands are inactive
Highly hindered alkenes and ethylene are not hydrogenated by the catalyst
 Wilkinson’s Catalyst

Reductive Elimination Oxidative Addition

Ligand Dissociation
Ligand Association

Migratory Insertion
Alkene Coordination
 Hydroformylation

A less common, but more appropriate name is hydrocarbonylation

Both cobalt and rhodium complexes are used as catalysts.

Alkene isomerization, alkene hydrogenation and formation of branched aldehydes are
the possible side reactions.

Cobalt catalysts operate at 150 ºC and 250 atm, whereas Rhodium catalysts operate at
moderate temperatures and 1 atm.
Rhodium catalysts promotes the formation of linear aldehydes. Cobalt catalysts do so if
modified with alkylphosphine ligands.
 Hydroformylation

Reductive Elimination Ligand Dissociation

Oxidative Addition
Alkene Coordination

Ligand Association
Migratory Insertion Ligand Association
Migratory Insertion
 Monsanto Acetic Acid Synthesis

All three members of the group 9 (Co, Rh and Ir) can catalyze this reaction.
A cobalt complex was initially used, which was replaced with the rhodium complex
later on.

Methanol initially reacts with hydroiodic acid to give methyliodide and H2O.
Methyliodide reacts with the 16e- catalyst, which forms the rate-determining step.

The final product formed after the catalytic cycle is acetyl iodide, which is hydrolyzed
by water to acetic acid and HI.
 Monsanto Acetic Acid Synthesis

Reductive Elimination Oxidative Addition

Migratory Insertion
η5 to η3 haptotropic shift
Indenyl Effect
CoBr2(CO)L2 ⇌ CoBr2L2 + CO