CML101

Introduction to Chemistry

Semester I, 2022-23

Inorganic Lecture-06
14-12-2022, Wednesday
 Summary of Lecture-05
Uncommon binding modes of CO

The effect of electron density on the metal center

(i) charge on the metal center

(ii) donor/acceptor ability of the other ligand(s) attached to the metal

(iii) size of the metal

(iv) electronegativity

A question was solved

 Preparation of Metal Carbonyl
Complexes
There are basic ways to prepare simple homoleptic transition metal

carbonyl complexes

Direct reaction of metals with CO

Reductive carbonylation of metal salts

Direct Reaction of Metals with CO
Only a few of the metal carbonyls can be prepared by this method

Iron and nickel can react with CO and afford nickel tetracarbonyl and

iron pentacarbonyl, respectively

1 bar, 25 °C
Ni + 4 CO Ni(CO)4

100 bar, 150 °C

Fe + 5 CO Fe(CO)5

Pure iron that has no surface oxides can react at room temperature

and 1 bar with CO

Nickel tetracabonyl was discovered by Lugwig Mond (1890) and it is

used for the production of pure nickel (Mond process)

 Reductive Carbonylation
This is the most widely used method for the preparation of

homoleptic/binary metal carbonyls

Here, metal carbonyls are prepared through the reduction of their

metal salts with reducing agents in an atmosphere of CO

Usually used metal salts are metal halide or acetates

Al, Na, Zn, Grignard reagent, trialkylaluminium, and so forth, are used

as reducing agents.

If metal oxides are used, CO works as a reducing agent and gets

oxidized to carbon dioxide

Look at the following examples:

 Reductive Carbonylation
C6H6, AlCl3
CrCl3 + Al + 6 CO Cr(CO)6 + AlCl3
300 bar, 140 °C

diglyme
MoCl5 + 5 Na + 6 CO Mo(CO)6 + 5 NaCl
62 bar, -10 -25 °C

Et2O, 67 °C
WCl6 + 3 Zn + 6 CO W(CO)6 + 3 ZnCl2
50 atm

(iso-Pr)2O
2 Mn(OAc)2 + 10 CO + AlEt3 Mn2(CO)10 + Al(OAc)3 + C4H10
207 bar, 80-100 °C

DME
2 Mn(OAc)2 + 4 Na + 10CO Mn2(CO)10 +NaOAc
165 °C, 240 bar

MeOH
3 Ru(acac)3 + 12 CO + 4.5 H2 Ru3(CO)12 + 9 MeC(O)CH2C(O)Me
150 °C, 155 atm
 Reductive Carbonylation
MeOH
OsO4 + CO Os3(CO)12 + 4 CO2
125 °C/75 atm

215 atm
Re2O7 + 17 CO Re2(CO)10 + 7 CO2
290 °C

toluene
RuO2. x H2O + CO Ru3(CO)12 + CO2
20 atm, 160 °C

1900 atm
CoO + CO Co2(CO)8 + CO2
80 °C

2000 atm
Fe2O3 + CO Fe(CO)5 + CO2
225 °C

2000 atm
MoO3 + CO Mo(CO)6 + CO2
300 °C
 A Few Reactivity of Metal
Carbonyls

Reactions of carbonyl compounds

Substitution reaction

Oxidative decarbonylation

Addition to CO

Reduction
 Substitution Reaction
This is the most common reactivity of metal carbonyls, where the CO

ligands are substituted by other suitable ligands

Carbonyl compounds can be activated for the cleavage of M-CO bond

either thermally of photochemically

In the metal carbonyls with 18 electrons, this reaction proceeds

through a dissociative mechanism

Metal carbonyls with 16/17 electrons take up the associate pathway

Associative pathway is faster than the dissociative pathway

 Substitution Reaction
Thermally, Lewis bases, arenes, and olefins can be substituted for

the CO ligands

Generally, it is very difficult achieve complete substitution

Substitution under either thermal conditions leads usually to the

formation of a mixture of products

 Substitution Reaction
Therefore, the usually followed activation method is to intermediately

introduce labile ligands such as tetrahydrofuran, etc.

Later, these ligands are replaced by the desired ligands under mild

reaction conditions
OC
OC CO
30°C, 100 min
Cr(CO)6 Cr
THF, 150 W, h  O
OC
CO

OC

ligroin, reflux 9 hrs OC

Cr(CO)6 + Cr
OC
CO
 Substitution Reaction
Few other M(CO)n transfer reagents are: (THF)Mo(CO)5, (CH2Cl2)Cr(CO)5,

M(CO)4(norbornadiene) (where M = Mo, W) and Fe(CO)3(cyclooctadiene)

These are prepared under thermal/photochemical conditions through the

direct reactions of homoleptic metal carbonyl with the corresponding

solvents/reagents.
Photochemical Substitution
W(CO)6 + PPh3 h W(CO)5(PPh3) + CO

Fe(CO)5 + h
Fe(CO)3 + 2CO

Mn(CO)5 h
CO Mn(CO)4
 Oxidation by Halogens
This reactivity leads to carbonyl halides

Mn2(CO)10 + Cl2 2 Mn(CO)5Cl

Mn2(CO)10 + Br2 2 Mn(CO)5Br

Fe(CO)5 + Br2 Fe(CO)4Br2 + CO

Fe(CO)5 + I2 Fe(CO)4I2 + CO
 Nucleophilic Addition to CO
Here, the nucleophilic addition occurs at the electron deficient

carbon atom of the carbonyl ligand attached to the metal

In organomeallic chemistry, it is a powerful tool, and is called as Hieber base

reaction
 Nucleophilic Addition to CO
Another example:

The reaction of [HFe(CO)4] with H+ leads to [H2Fe(CO)4]

Reduction: Synthesis of carbonyl
anions
Reduction of carbonyl compounds or the reactions of carbonyl

compounds with strong nucleophilies

When reducing agents like Na/Hg is used, mono- (or) dianionic

carbonyl complexes are usually obtained

But, usage of strong reducing agents like Na/HMPA, Na/liq. Ammonia,

and so forth, are used, highly reduced anions with charges up to 4

can also be obtained

Reduction: Synthesis of carbonyl
anions

Potassium salt of
acetylenediolate, K2(O—CC—O)
 Collman’s Reagent
As we discussed earlier, Na2Fe(CO)4 is called as Collman’s reagent

Using this reagent, functionalization of the organic halides in various

ways is possible

R O
RX
Na[RFe(CO)4 CO C
CO
Na2Fe(CO)4 RCOCl OC Fe
CO
CO
 Collman’s Reagent

R O
H+ C X2
RCHO CO RC(O)X
OC Fe
CO
R'X CO O2
O
R C R' H+ RCOOH