Organometallic Chemistry (CY501 and CHI441)

Dr. Samya Banerjee

I will let you teach me these…… I am your student

Organic Chemistry

Inorganic Chemistry

Organometallic Chemistry

Metallo-organic compounds

1st book to read:

2. COURSE TOPICS::
Synthesis, characterization and properties of transition metal complexes with π- bonding ligands (CO, NO,
PR3, AsR3, alkene, alkyne, allyl, diene, arene, cyclopentadiene, N2, O2) [10 Lectures]

Synthesis, characterization and properties of transition metal σ-bonded complexes (hydride, alkyl, aryl) )
[04 Lectures]

Synthesis, characterization and properties of metalo carbenes, carbynes including metal ligand multiple bond
with hetero atoms [04 Lectures]

Reaction of organometallic complexes (oxidative addition, reductive elimination, insertion, nucleophilic and
electrophilic addition and abstraction, coupling) [08Lectures]

Catalytic application of organometallic complexes (hydrogenation, oxidation, CO insertion,

hydroformylation, Monsanto process, Wacker process, polymerization, metathesis, C-H bond activation,
coupling reactions) [13Lectures]
 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 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 *

Which compounds are organometallic?

 C always more electronegative compared to M

According to the main journals

Organometallic complex/compound must have “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)”.
 Zeise’s Salt
William Christopher Zeise,
Danish pharmacist
Discovery 1827

Crystal Structure ~
150 years later

Organometallics, 2001, 20, 2.

 Diethyl zinc

First σ bonded Organometallic Compound

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

 Robert Bunsen’s (Bunsen

burner) student synthesized
diethyl zinc
 Accidental synthesis
 Trying to make ethyl radicals.
 Metal carbonyls
Ludwig Mond
Founded the Imperial
chemical industry, UK
Father of M-CO Chemistry
‘Mond nickel company’ made ca. 3000
tons of nickel (in 1910)
Purity = 99.9%

1890-1930 textbooks
 Grignard Reagent
 He was a Ph.D student
François Auguste  Discovered the Grignard reaction in
Victor Grignard 1900
 Awarded the Nobel Prize in 1912
(Chemistry).
 Sandwich complexes and Hapto ligation

, hapto symbol, (with a numerical superscript) indicates the connectivity between

the ligand and the metal atom/ion.

Sandwich (5-C5H5)2Fe (6-C6H6)2Cr

More examples:
1-R, 1-Ar 2-C2R4 1-allyl, 3-allyl, 4- Cb, 5-Cp, 6-C6H6 8-C8H8 2-C60,
5-R5C60.
 18 electron rule
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”.

Conditions favoring the 18 electron rule: (1) an electron rich metal (one
that is in a low oxidation state) and (2) ligands that are good -acceptors

The symbol  indicates bridging normally we have 2 and rarely 3

bridging

Examples:
2-CO, 3-CO, 2-CH3, 2-H, 2-Cl, , 3-Cl, 2-OR, 2-PR2, 2-NR2
Methods of counting: Neutral atom & 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
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

 Lets try the following

Ni(CO)4
Fe(CO)5
Co2(CO)8
Fe2(CO)9
Mn2(CO)10
[Co(CO)5]z Determine Z

Neutral atom method: Metal in zero oxidation state

Oxidation state method: First determine the oxidation state of the metal
(consider the number of anionic ligands and overall charge of the complex)
 18 electron rule-Exceptions
Cl
for each Pd: Ox. state
Pd Pd , Cl
Ox. State: 2 Cp-, 1 H-, 1 Cl- Cl
H  Zr(IV) Pd(II)
Zr bridging by lone
Cl
pairs on Cl; d: 10 (4d10 5s 0) - 2 = 8
d: 4 (4d25s2) -4=0 each Cl acts as a
2-electron, mono
negative ligands to electron count:
electron count: 2 Cp-: 12
one of the Pd's,
H- : 2 and a 2-electron : 4e-
Cl- : 2 neutral donor ligand
Zr : 0 like PPh3 to the other
Cl : 2e-
16 e-, unsaturated
Cl : 2e-
8e- + d8 = 16e-
unsaturated
 18 electron rule-Exceptions

 Square planar organometallic complexes of late transition metals

 Few organometallic complexes of the early transition metals (e.g. Cp2TiCl2,

WMe6, Me2NbCl3, CpWOCl3)

 Possible reason: Some of the orbitals of these complexes are too high energy
for effective utilization in bonding or the ligands are mostly  donors

 Sterically bulky ligands force complexes to have less than 18 electrons

 Not applicable for organometallic compounds of main group elements,

lanthanide, actinide and organometallic clusters (6 Metal atoms and more) .
Metal carbonyls

 Coordination number:
Normally 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 organometallic
compounds  Used as efficient catalysts in Chemical Industry

 M-C  bonding is well

understood. Hydroformylation
 CO is one of the strongest Alkene to Aldehyde
 acceptor ligands. Back
bonding ( bonding) and
Methanol to Acetic acid
variation in electronic
properties of CO can be
monitored efficiently by
Infrared spectroscopy
 Synthesis of Metal Carbonyls
Direct carbonylation
Reductive carbonylation
 Molecular Orbital diagram of CO
Why does CO bind to the metal through carbon
atom?
What makes it a good  acceptor ?

 The highest occupied molecular orbital

(HOMO) of CO is carbon based.
 The * antibonding orbital (lowest
unoccupied molecular orbital, LUMO) is
of comparatively lower energy.
Bonding in Carbonyl complexes
Bonding in Carbonyl complexes
Bonding in Carbonyl complexes
Bonding in Carbonyl complexes
 Quiz-1 (18 points)
Following organometallic complexes are stable and has a second row transition metal (M). Find out the
“M”

4 X 2 = 8 Points

Calculate the no of valence electrons for each complexes. 5 X 2 = 10 Points

Bonding in Carbonyl complexes
Bonding in Carbonyl complexes
Bonding in Carbonyl complexes
Bonding in Carbonyl complexes
Bonding in Carbonyl complexes
 Characterization of Carbonyl complexes
 Single crystal X-ray diffraction

 Elemental analysis

 Mass spectroscopy

 Infrared (IR) spectroscopy

 Infrared (IR) spectroscopy

 Vibrational spectroscopy

 Region: 4000 – 400 cm-1

https://www.youtube.com/watch?v=1PQqDfJKXvA
 Infrared (IR) spectroscopy
 Most common spectroscopic techniques used by chemists

 It is absorption measurement of different IR frequencies by a compound placed in path of

IR beam

 Main goal: determination of the chemical functional groups in a given sample

 Functional groups are identified based on vibrational modes such a stretching, bending etc.
Different vibrational modes absorb characteristic frequencies of IR radiation.

cm-1
 Infrared (IR) spectroscopy
 IR spectrophotometer: Instrument that passes IR
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 IR radiation on the
horizontal axis.
 Absorption of light/radiation lowers the
percentage transmittance value.
Characterization of Carbonyl complexes
 IR spectra of Carbonyl complexes

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

2000 cm-1 2018, 1826 cm-1 1620 cm-1

IR spectra of Carbonyl complexes

 The range in which the

band appears decides
Terminal
bridging or terminal.

 Number of bands is only

Bridging related to the symmetry
of the molecule

Terminal
 IR spectra of Carbonyl complexes
Factors which affect CO stretching frequencies

1. Charge/ Oxidation state of the metal

2. Effect of other ligands
 IR spectra of Carbonyl complexes
Variation in  CO (cm–1) of the first row transition metal  As the electron density on a metal centre
carbonyls increases, more -backbonding to the CO
Free CO ligand(s) takes place.
2143

Ni(CO)4  This weakens the C–O bond further as

2057 more electron density is pumped into the
Co(CO)4- Co2(CO)8 empty * anti-bonding carbonyl orbital.
1890 2044 (ter)

[Fe(CO)4]2- Fe(CO)5  This increases the M–C bond order and

1815 2030 reduces the C-O bond order. That is, the
[Mn(CO)4]3- Mn(CO)6 + Mn2(CO)10 resonance structure M=C=O becomes
1600 2098 2013
more dominant.
[Cr(CO)4]4- Cr(CO)6
1462 2000

V(CO)6¯ V(CO)6
1860 1976

Ti(CO)62- More back bonding

1747
IR spectra of Carbonyl complexes
 IR spectra of Carbonyl complexes
PR3  CO, (cm–1) PR3  CO, (cm–1)

P(t-Bu)3 2056.1 PPh2(C6F5) 2074.8

PCy3 2056.4 P(OEt)3 2076.3

P(i-Pr)3 2059.2 P(p-C6H4-CF3)3 2076.6

PEt3 2061.7 P(OMe)3 2079.5

P(NMe2)3 2061.9 PH3 2083.2

PMe3 2064.1 P(OPh)3 2085.3

PBz3 2066.4 P(C6F5)3 2090.9

P(o-Tol)3 2066.6 PCl3 2097.0

PPh3 2068.9 PF3 2110.8

PPh2H 2073.3 P(CF3)3 2115.0

Reactions of Metal Carbonyls
Reactions of Metal Carbonyls
 Metal Nitrosyls

NO
Metal Nitrosyls
 Metal Nitrosyls

Which linkage is stronger ? M-CO or M-NO ??

 Bridging Nitrosyls

NO
Bent Metal Nitrosyls
Metal- Sandwich compounds

Hapticity of sandwich
compounds varies
 Importance of Metal- Sandwich compounds
 Makes a metal ion soluble in hydrocarbon solvents. E.g. Ferrocene is
soluble in hexane while Fe2+ as such is not. Outcome: a hydrocarbon
soluble additive/catalyst

 Steric protection at metal site; helpful for catalytic

applications

Ferrocene: Smoke suppressant

fuel additive
 Cyclopentadienyl (Cp-)
 Most important and well studied among all the polyenyl ligands
 Firmly bound to the metal
 Stabilising ligand for many complexes.

 Cyclopentadiene (C5H6) is a weak

acid with pKa of ca. 15
 Deprotonated by strong base or alkali
metals to generate Cp-

(5-Cp)(3-Cp)W(CO)2
Synthesis of Cp- based sandwich compounds
Bonding of metallocene
Frontier orbitals are neither
strongly bonding nor strongly
antibonding. As a result, metallo-
cene compounds often diverge
from the 18 electron rule.
Bonding of metallocene
If the complex has more than
18 electrons, the e1u orbitals,
which are slightly antibonding
become occupied. This
lengthens the M-C distance.
 Bonding of metallocene

(η5-Cp)2M e- count M-C(pm) ΔHdissoc.*

Fe 18 206.4 1470 kJ/mol
Co 19 211.9 1400
Ni 20 219.6 1320

* ΔHdissoc refers to the complex dissociating to M2+

and 2C5H5-
 Reactions of Ferrocene
Ferrocene undergoes electrophilic
substitution reactions
Many of its reactions are faster than
benzene
Necessary requirement:
Electrophile should not be oxidizing
Acetylation

3.3 x 106 times faster than benzene

 Reactions of Ferrocene
Chloromercuration

109 times faster than benzene

Mannich reaction

Does not happen with benzene;

only with phenols/anilines
Lithiation reaction
Lithiation and 1,1’-di-lithiation – access to many derivatives
 Other Cp complexes

Me Me
Me Si
Fe Si 130 °C
Fe
Me
n

M. Wt: 3.4 X 105

 Transition Metal (Tm) hydrides

 Pure hydride complexes are rare

 Few pure poly hydrides such as [ReH9]2- have only M and H

Why we say hydride ?

 In Tm(CO)nH, EN of the “Tm” is > H !

 TmH may give H+ and [Tm]-

 Still it called as hydride, implies that it is H- but behaves like H+

 Transition Metal (Tm) hydrides
Hieber (1895-1976) first made TmH

Fe(CO)5 + 3NaOH Na[HFe(CO)4] + Na2CO3 + H2O

[(CO)4Fe-CO-OH)]- [HFe(CO)4]- + CO2

Synthesis:

Reduction of Sulfide: CoS + H2 + CO HCo(CO)4 + H2S

Reaction with oxide: OsO4 + H2 + CO H2Os(CO)4 + H2Os2(CO)8

Reduction of Chlorides: RuCl2(PPh)4 + H2 HRuCl(PPh)3

 Transition Metal (Tm) hydrides
Oxidative M-M cleavage by H2
Mn2(CO)10 + H2 HMn(CO)5
Protonation

M-H stretch at 2200-1700 cm-1……….Difficult to assign…..Why ??

HCo(CO)4 …………… 1934 cm-1

HMn(CO)5 ………….. 1783 cm-1

 Transition Metal (Tm) hydrides
 NMR: Highly useful Reactions
 But some time difficult to assign the
peak-peak intensity is very less
 Signals from H in Tm – H can be very
broad
 Usually upfield -3 to –24 ppm Why ?
δ, depends on dn configuration and
other coordinating ligand
 Difficulties in X-ray structure
 Difficult to located from X-ray diffraction data

Low electron density makes it highly difficult to

locate H Predict the Product

“Swallowed up by the metal’s electron

density..” Too close to the metal

Neutron diffraction studies

Low temp. X-ray data collection

Tm-H are important organometallic compounds as they are involved in many

crucial steps of numerous catalytic reactions
 Carbene
What is this ?

Electronic structure ??

Type ???

S. Banerjee et al., Inorg. Chem. 2020, 59, 11253−11258.

 Metal Carbenes
Fischer carbene

Bonding is more like CO

Schrock carbenes

What is the difference ?

 Metal Carbenes

What about the oxidation state of metal ?

M-C bond strength ??

Metal Carbenes
Metal Carbenes
 Metal Carbenes
 Carbene carbon of Fischer carbene is
electrophilic/ nucleophilic ?

 Fischer carbene shows similar reactivity

to that of carbonyl compound

 Many of the reactions can be

understood using carboxylic equivalent
structure

 Cr(CO)5 moiety is a strong electron

withdrawing group making the α-proton
acidic
Metal Carbenes

Dötz reaction
 Metal Carbenes

Tebbe’s Reagent: Protected :CH2

 Metal Carbenes

Intermediate Carbene: In between Fischer and Schrock

 Metal Carbenes

Chem. Commun., 2014, 50, 10355--10375

 Quiz-2 (10 Points)
1. Explain all kinds of M-NO bond formation in metal nitrosyl? 4 Points

2. Which of the below is the correct increasing order of CO stretching frequency.

Provide explanation also 2 Points

(a) Ni(CO)4 > Co2(CO)8 > Fe(CO)5 > [Mn(CO)4]3-

(b) Co2(CO)8 > Ni(CO)4 > Fe(CO)5 > [Mn(CO)4]3-

(c) [Mn(CO)4]3- > Ni(CO)4 > Fe(CO)5 > Co2(CO)8

(d) Fe(CO)5 > Co2(CO)8 > Ni(CO)4 > [Mn(CO)4]3-

3. Identify X and Y 2+2 Points

Metal Carbynes

New discovery is always accidental

Metal Carbynes
 NHC (N-heterocyclic carbenes)

 Delocalization of the N1 and N3

lone pairs into the empty p orbital
 Much more stable compared to carbine of the carbene carbon
stabilizes the singlet state by > 80
 Initial concept: Steric hinderence kcalmol-1 relative to the triplet
state.
 NHC (N-heterocyclic carbenes)
New and hot area of research, Started from ca. 1990

X-ray structure: N-C bond is longer compared to parent imidazolium

Better electron donor: Even better than most basic phosphines

NHC (N-heterocyclic carbenes)
NHC (N-heterocyclic carbenes)
 Metal-alkenes
Zeise’s Salt ??
C C
M  M *
C C

donation from  back donation to *

Extend of back bonding

matters a lot……….
Metal-alkenes
Metal-alkenes
Metal-alkenes