AJELIAS L2‐S5

Infrared Spectroscopy‐ A spectro‐analytical tool in chemistry 

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.
 AJELIAS L2‐S6

Infrared Spectroscopy‐ Spectra of Metal Carbonyls  

CO OC CO
OC

OC Mn Mn CO

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

The number of 
bands is only 
related to the 
symmetry of the 
molecule

O O
C
bridging
OC C CO

OC Fe Fe CO
OC C CO
O

terminal
 AJELIAS L2‐S7

Terminal versus bridging carbonyls

O
M O
C
C
C M
M M M
O
M
terminal bridging μ 2 bridging μ
ν 3
CO 2120-1850 cm-1
1850-1700 cm-1 1730-1620 cm-1

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

 AJELIAS L2‐S8
Factors which affect νCO stretching frequencies
1.Charge on the metal
2. Effect of other ligands
Variation in νCO (cm–1) of the first row transition
metal carbonyls
free CO
2143 As the electron density on a 
Ni(CO)4 metal centre increases, 
2057 more π‐back‐bonding to the 
Co(CO)4- Co2(CO)8 CO ligand(s) takes place. 
1890 2044(av, ter) This weakens the C–O bond 
[Fe(CO)4]2- Fe(CO)5 further as more electron 
1815 2030 density is pumped into the 
[Mn(CO)4]3- Mn(CO)6 + Mn2(CO)10 empty π* anti‐bonding 
1600,1790 2098 2013 (av)
carbonyl orbital.  This 
[Cr(CO)4]4- Cr(CO)6 increases the M–C bond 
1462,1657 2000
order and reduces the 
V(CO)6¯ V(CO)6
1860 1976
C‐O bond order. That is, the 
resonance structure M=C=O 
Ti(CO)62-
1747 becomes more dominant.

M C O M C O
ν CO Higher ν CO Lower
More back bonding
 AJELIAS L2‐S9

Other spectator ligands: Phosphines 

PR3 νCO, (cm–1) χ(cm–1) PR3 νCO, (cm–1) χ(cm–1)

Δ νCO wrt Δ νCO wrt
P(t-Bu)3 P(t-Bu)3
P(t-Bu)3 2056.1 0.0 PPh2(C6F5) 2074.8 18.7
PCy3 2056.4 0.3 P(OEt)3 2076.3 20.2
P(i-Pr)3 2059.2 3.1 P(p-C6H4-CF3)3 2076.6 20.5

PEt3 2061.7 5.6 P(OMe)3 2079.5 23.4

P(NMe2)3 2061.9 5.8 PH3 2083.2 27.1
PMe3 2064.1 8.0 P(OPh)3 2085.3 29.2
PBz3 2066.4 10.3 P(C6F5)3 2090.9 34.8
P(o-Tol)3 2066.6 10.5 PCl3 2097.0 40.9
PPh3 2068.9 12.8 PF3 2110.8 54.7
PPh2H 2073.3 17.2 P(CF3)3 2115.0 58.9
PR3
Lowest CO stretching frequency Highest CO stretching frequency
Most donating phosphine Ni Least donating phosphine
best σ donor CO best π acceptor
OC
CO
 AJELIAS L2‐S10

Effect of a ligands trans to CO

Effect of different co-ligands on νCO (cm-1) of

Mo(CO)3L3
Complex ν CO cm–1
(fac isomers)
Mo(CO)3(PF3)3 2090, 2055
More back bonding =
CO More lowering of 
Mo(CO)3(PCl3)3 2040, 1991
L CO the C=O bond order = 
Mo Mo(CO)3[P(OMe)3]3 1977, 1888
More lower ν CO 
L CO
L Mo(CO)3(PPh3)3 1934, 1835 stretching frequency
Mo(CO)3(NCCH3)3 1915, 1783
Mo(CO)3(dien)* 1898, 1758
Mo(CO)3(Py)3 1888, 1746

With each negative charge added to the metal centre, the CO stretching 
frequency decreases by approximately 100 cm–1.

The better the σ 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.
 AJELIAS L2‐S11
Synthesis of Metal Carbonyls

Direct carbonylation

Reductive carbonylation
 AJELIAS L2‐S12
Reactions  of Metal Carbonyls
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

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

Fe(CO)5 + I2 Fe(CO)4I2
Photochemical substitution
hν W(CO)5(PPh3) + CO
W(CO)6 + PPh3
In the presence of  
Fe(CO)5 + hν UV radiation a 
Fe(CO)3 + 2CO
monodentate
ligand displaces 
only one CO unit
 AJELIAS L2‐S13
Reactions  of Metal Carbonyls

Nucleophilic addition to CO

R OLi R OCH 3
CO
C C
OC CO OC
OC CO [Me 3O]BF 4 CO
W RLi W
W
OC CO OC
ether OC CO CO
OC OC
OC
Fischer Carbene
Carbenes are catalysts
for olefin metathesis

Migratory insertion of CO
Me
Me O
C
OC CO
CO
OC CO
Mn
Mn
OC CO high pressure
OC CO
OC
OC
 Problem solving ‐ synthesis

Give a scheme for the synthesis of Mn(CO)4(PPh3)[C(O)CH3] starting from 
Manganese acetate, Mn(OAc)2.

high temp
2 Mn(OAc)2 + 4 Na + 10 CO high pressure Mn2(CO)10 + 4 NaOAc

Mn2(CO)10 + 2 Na 2 NaMn(CO)5

NaMn(CO)5 + CH3I CH3Mn(CO)5

CH3Mn(CO)5 + CO CH3C(O)Mn(CO)5 ( migratory insertion)
CH3C(O)Mn(CO)5 + PPh3 CH3C(O)Mn(CO)4PPh3
hv
Or at step 3 direct reaction with acyl chloride instead of MeI. Step 1 other
reducing agents e.g. AlEt3 can also be used.
 AJELIAS L2‐S14

Metal‐ Sandwich compounds

Hapticity of sandwich 
compounds varies from 1‐8
 AJELIAS L2‐S15

Why metal – sandwich compounds are important? 
1. Transition metal/ metal ion embedded inside an organic matrix: Makes a metal ion soluble
even in hydrocarbon solvents. E.g. Ferrocene is soluble in hexane while Fe2+ as such is not.
Outcome: a hydrocarbon soluble additive/catalyst

2. Coordination to an electropositive metal often changes the reactivity and electronic 
properties of the π system bound to it  (benzene vs ferrocene)

3. A stericially protected metal site where a wide range of catalytic applications are possible  
on the. e.g alkene polymerization

4. Metal sandwich compounds are excellent substrates to make planar chiral compounds. 
Applications as chiral catalysts in asymmetric catalysis 

X X
Y Y

Fe Fe

Planr chirality:
Non‐ super‐imposable 
mirror images
 AJELIAS L2‐S16

Cyclopentadienyl (Cp−)

• Cyclopentadienyl (Cp−)  the most important of all the polyenyl ligands

• It gets firmly bound to the metal  
• generally inert to nucleophilic reagents. 
• used as a stabilising ligand for many complexes. 

M M

η1 η3 η5
Least m ost
com m on com m on
(η5‐Cp)(η3‐Cp)W(CO)2

•Neutral cyclopentadiene (C5H6) is a weak acid with a pKa of around 15 

•Deprotonated with strong base or  alkali metals to generate the anionic Cp−
 AJELIAS L2‐S17

Synthesis of Cp (C5H5‐) based sandwich compounds

FeCl2 + 2 C5H6 + 2 Et2NH Cp2Fe + 2 [Et2NH2]Cl

RuCl3(H2O)n + 3C5H6 + 3/2 Zn Cp2Ru + C5H8 + 3/2 Zn2+

H 2O 2 CpTl + K2SO4 + H2O

2 C5H6 + 2 KOH + Tl2SO4
(poisonous)
CpTl + Mn(CO)5Cl CpMn(CO)3 + TlCl + 2 CO
CpTl based chemistry is not practiced nowadays due to toxicity

H
H

180°C
Na
2 NaCp + H2
cracking
H H
H H
dicyclopentadiene
MCl2 + 2 NaCp Cp2M [ M = V, Cr, Mn, Fe, Co]
Solvent: THF, DME, Liquid NH3 etc
 AJELIAS L2‐S18

Fe Ferrocene: synthesis

Lab Synthesis
Fe + 2 (R 3NH)Cl FeCl2 + 2 R 3N + H 2
FeCl2 + 2 C 5H 6 + 2 R 3 N Cp 2Fe + 2(R 3NH)Cl

FeCl2 + 2 NaCp Cp2Fe

 AJELIAS L2‐S19
Reactions of Ferrocene
Ferrocene undergoes electrophilic substitution reactions. Many of its reactions are 
faster than similar reactions of benzene
Necessary requirement: The electrophile should not be oxidizing in nature

Fe
I2 Fe
I3

p- benzoquinone
FeCp2 + HBF4.OEt2 [FeCp2][BF4]
Et2O

FeCl3
FeCp2 + NH4PF6 [FeCp2][PF6]
H2O/Acetone

The oxidized Cp2Fe+, ferrocenium cation, will repel the electrophile away. Therefore direct nitration, 

halogenation and similar reactions cannot be carried out on ferrocene. 

Acetylation

H3C(O)C CH3C(O)Cl C(O)CH3 C(O)CH3

Ac2O/ H3PO4
60 min, 50 °C AlCl3(1:2:2) C(O)CH3
Fe Fe Fe
Fe
C(O)CH3
traces
90 % 90 %

3.3 x 106 times faster than benzene
 AJELIAS L2‐S20

Chloromercuration (hazardous)
Hg(OAc)
HgCl
Hg(OAc)2
LiCl
Fe Fe Fe
Br2/I2

Br, I derivatives

109 times faster than benzene
Mannich reaction
H2
C NR2
HCHO/R2NH
Fe Fe
H3PO4
Does not happen with benzene; only with 
phenols/anilines

Lithiation reaction
Li Li
N
t-BuLi n-BuLi
Fe Fe Fe
TMEDA
Li N

(3:2 adduct)
Does not happen with benzene; only with 
bromobenzene
 AJELIAS L2‐S21
Lithiation and 1,1’‐di‐lithiation – access to range of new derivatives

Li
CO2/H+ Cl3Si
HOOC SiCl4
Fe
Fe Fe

O) 3B
( Bu
1/8 S
H+ 8
(HO)2B
I2 SLi
Fe
Fe
I
Fe NaCN CN
Fe

dppf

[1]ferrocenophane
 AJELIAS L2‐S22

Polymers with ferrocene in the backbone

Me Me
Me Si
Fe Si 130 °C Fe
Me
n

M. Wt: 3.4 X 105

Bisbenzene chromium:  Prepared by Fischer and Hafner

Cr AlCl4 Na2S2O4 Cr
3 CrCl3 + 2 Al + AlCl3 + 6 C6H6 3
KOH
 Problem solving ‐ synthesis

Starting  fro m ferrocene show  minimum  number of steps for  preparing 
1,1’‐ ferrocene dicarboxylic acid