Unit 3 Metal Carbonyl Compounds-I

UNIT 3

METAL CARBONYL
COMPOUNDS-I

Structure
3.1 Introduction 3.5 Properties of Mononuclear
and Polynuclear Carbonyl of
Expected Learning Outcomes
3d Metals
3.2 EAN Rule and 18 Electron
3.6 Summary
Rule (as applied to Carbonyls)
3.7 Terminal Questions
3.3 Preparation - Direct
Combination, Reductive 3.8 Answers
Carbonylation

3.4 Structure (Based on VB

Approach) and Properties

3.1 INTRODUCTION
In the previous unit, you were introduced to organometallic compounds. In this
unit you will study metal carbonyl compounds. The details of EAN (Effective
Atomic Number) Rule and 18 Electron Rule as applied to carbonyls will be
discussed. This will be followed by preparation of metal carbonyls through
direct combination and reductive carbonylation. Finally the structure of metal
carbonyls and their properties with special reference to mononuclear and
polynuclear carbonyls of 3d metals will be dealt with.

In the next unit, you will learn more about metal carbonyl compounds specially
their bonding and IR stretching frequency data. So in this way, you will be
learning all about the metal carbonyl compounds through units 3 and 4 of this
course.

Expected Learning Outcomes

After studying this unit you should be able to:

 understand EAN Rule and 18 Electron Rule as applied to carbonyls; 35

Block 1 Compounds of 3d Metals

 describe the preparation of metal carbonyls through direct combination

and reductive carbonylation;

 understand the structure of metal carbonyls based on Valence Bond

approach; and

 describe the properties of mononuclear and polynuclear carbonyl of 3d

metals.

3.2 EAN RULE AND 18 ELECTRON RULE (AS

APPLIED TO CARBONYLS)
Sidgwick first tried to The first carbonyls discovered were those of iron, cobalt and nickel. Their
explain bonding in formulae, as well as the formulae of their carbonyls were derived later. A large
transition metal number of metal carbonyls, including many anionic and cationic species,
complexes. He then nitrosyl, hydrogen, and halogen-substituted metal carbonyls and small metal
extended octet theory cluster carbonyls, conform to the 18 electron rule. This rule can also be
of Lewis to
formulated in terms of the total number of electrons around the metal in which
coordination
compounds.
case this number is usually found to be 36, 54, or 86, corresponding to the
atomic numbers of the noble gases Kr, Xe, and Rn. The metals are then said
to have the effective atomic number of the noble gases, or to obey the EAN
rule. Because the pseudo-noble gas valence shells of Kr, Xe, and Rn contain
18 electrons, it is simpler just to count valence shell electrons.

EAN is referred to as Effective Atomic Number. Complexes of transition

metals with -acid ligands, and their organometallic compounds generally
obey the EAN rule. The central metal atom appears to have acquired the
configuration of a noble gas by transference or sharing of electrons. The total
number of electrons which the metal ion appears to have around itself is called
the EAN of the metal and when this equals 36(Kr), 54(Xe) or 86(Rn) the EAN
rule in said to be followed. Well, you can also say that when the metal
achieves an outer shell configuration of (n-1)d10ns2np6, there will be 18
electrons in the valence shell and a closed stable configuration. This is known
as the 18 electron rule which has the advantage of being the same for all rows
in the periodic table so that you need not remember the atomic numbers of all
noble gases. This is another way of saying that all the bonding capacity of the
metal is utilised. This rule allows the systematization of much of the structural
chemistry of transition metal organometallic compounds. The transition metal
complexes studied earlier are classical complexes and contain metal in the
oxidation states + 2 or more and involve ligands which are N or O donors or
halides. However in organometallic compounds, particularly the carbonyls
where the EAN rule is followed, the metal is in low oxidation state, may be
zero or even negative.

You know that when bonds are formed the orbitals involved should be
matched in energy. This is noted in the middle of the series and for metals in
low oxidation state. Increasing the oxidation state changes the slope of the
binding energy versus atomic number line and increases their separation. So
for sufficiently positive oxidation state (greater than or equal to 2), the EAN
rule does not hold. Within its region of applicability the rule is a reliable guide
36 to molecular structure and stoichiometry.
Unit 3 Metal Carbonyl Compounds-I

In certain cases molecules having 16 valence electrons seem to be equally

stable. This is specially true for metals at the right corner of the transition
series, i.e. Rh, Pd, Ir, Pt. These elements have the least tendency to be six
coordinate and Ir(I), Pt(II) form many four-coordinate species.

In most cases the maximum coordination number is 6 and if each ligand

donates a pair of electrons, then the metal must have d6 configuration to follow
18 electron rule. Structure of such complexes are found to be roughly
octahedral. Metals with d8 system need 5 electron pairs and the expected
geometry is trigonal bipyramidal or square pyramid whereas metals with d10
configuration need 4 electron pairs and form tetrahedral or square planar
complexes. In case of 16 electron species they are generally square planar
and are invariably based on d8 metal ions. (VSEPR & Valence Bond Theory
may be recapitulated from BCHCT-131, Units 7 and 8).

The rule is used to predict the existence and number of metal-metal bonds.
Most stable metal carbonyls obey the rule. The steps to calculate the EAN of
metal carbonyl compounds is given below:

1. Firstly, you must count the number of electrons in the valence shell of
the metal atom. Depending on the charge of the metal in the complex ,
you have to add or subtract electrons.
2. Secondly, you have to check the number of electrons the organic ligand
formally contributes to the valence shell of the atom (in case of CO each
terminal ligand contributes two electrons and each bridging ligand
contributes one electron to each metal).
3. Next, if any conventional ligands are present then check the number of
electrons contributed to valence shell by them.
4. Each M-M bond donates one electron to each metal. So find out how
many electrons donated by metal-metal bonds (M-M) in complexes.
5. You must add all electrons checked in steps 1 to 4. This gives the EAN.

Metals with odd atomic number cannot satisfy the EAN (18 electron) rule by
simple addition of CO ligands, since the resultant entity will always have an
odd number of electrons no matter how many CO molecules are added. There
are several options open to these metals by which the 18 electron rule can be
satisfied. The simplest is the addition of one electron by a reducing agent to
form a carbonylate anion [M(CO)n]-.

There are some stable compounds with electrons other than 18. In such
compounds, the factors such as CFSE (you have already studied about CFSE
or the Crystal Field Theory in the previous course of CBCS, namely
BCHCT-137, Units 6 & 7) and nature of M-C bonding contribute to the stability
of the compound. Some of the metal carbonyl compounds of d block (Groups
9 & 10) obey 16 electron rule. V(CO)6 has 17 electrons and is therefore called
17electron- species. It readily completes 18 electron configuration by
accepting an electron from reducing agent. V(CO)6 is the only odd electron
carbonyl which does not dimerise. If it dimerises the coordination number of V
will be 7 which is not favourable. This is because it would then produce steric
hindrance. Ligand-ligand repulsion overcomes a weak V-V bond. 37
Block 1 Compounds of 3d Metals

Alternatively, the electron deficient species can bond covalently with an atom
or group which also has a single unpaired electron available, for example, H or
Cl: HM(CO)n or M(CO)nCl. Finally if no other species is available with which to
react, two moieties each with an unpaired electron can dimerize with resultant
pairing of odd electrons. The pairing of the odd electron on each metal atom in
the diamagnetic dimer results in a M-M bond. For example, Mn(CO)5 has 17-
electrons. Two molecules ‘share’ their odd electron, in order to form a Mn-Mn
bond. Consequently each Mn becomes an 18 electron species as shown
below:
- -
Mn 7e Co 9e
- -
5CO 10e 4CO 8e
- -
Charge 1e charge 1e
- - - -
[Mn(CO)5] 18e [Co(CO)4] 18e

The electron count shown above is for the neutral atom method. In the
-
oxidation state procedure, each metal would be considered as an M species
with additional electron, so in this case there would be no entry for the overall
charge.

The dimeric species, Mn2(CO)10 and Co2(CO)8, also are stable and are
diamagnetic. If it is assumed that each compound has a metal-metal single
(two-electron) bond, the electron count yields a total of 18 for each metal:
- -
2Mn 14e 2Co 18e
- -
10CO 20e 8CO 16e
- -
Mn-Mn 2e Co-Co 2e
- -
[Mn2(CO)10 36e Co2(CO)8 36e
- -
or 18e /Mn or 18e /Co

So you see, for each such counting of total number of electrons, we follow the
same method. Let us understand the 18 electron rule with the help of more
examples:

Example 3.1: Fe2(CO)9

-
2 Fe 16 e
-
9 CO 18 e
-
Fe – Fe bond 2e

Total Number of electrons 36

Electron for each Fe 36/2 = 18

Example 3.2: Ni(CO)4

-
Ni 10 e
-
4 CO 8e

Total Number of electrons for Ni(CO)4 18

38
Unit 3 Metal Carbonyl Compounds-I

Example 3.3: Fe(CO)5

-
Fe 8e
-
5 CO 10 e

Total Number of electrons for 18

Fe(CO)5

Example 3.4: Using the 18 electron rule as a guide find the value of n in
Co2(CO)n

2 Co 18 e

n CO 2n e

Co-Co 2e

Thus 18 + 2n + 2 = 36

2n = 16 : n = 8

So the formula is Co2(CO)8

Table 3.1: Contributions of ligands to electron counting

Terminal ligands Neutral atom Oxidation state

electron count electron count

Carbonyl (MCO) 2 2

Thiocarbonyl (MCS) 2 2

Phosphine (MPR3) 2 2

Amine (MNR3) 2 2
Dinitrogen (M N N) 2 2
H 2 2
Dihydrogen M
H

C 2 2
Alkene M
C

C 2 2
Alkyne* M
C

Isocyanide (MCNR) 2 2
:

Nitrosyl, bent (M N ) 3 2

O
Nitrosyl, linear (M N O) 1 2

Halogen (MX) 1 2

Hydrogen (MH) 1 2
39
Block 1 Compounds of 3d Metals

Alkyl (MR) 1 2
O 1 2
Acyl (M C R)

Aryl (M-C-R) 1 2

Amide (M-NR2) 1 2

Phosphide (M-PR2) 1 2

Alkoxide (M-OR) 1 2

Thiolate (M-SR) 1 2

Carbene = alkylidene 2 4
(M=CR2)

Carbene = alkylidene 3 6
(M=CR)

1 2

3 4

3 4

1 2

5 6

6 6

7 6

8 10

Bridging ligands
Carbonyl [M – (CO) – M] 2 2

Halogen (M –X– M) 3 4

4 4
C
Alkyne M M
C

Hydrogen (M – H – M) 1 2
40
Unit 3 Metal Carbonyl Compounds-I

Alkyl [M– (CR3) – M] 2 2

Amide [M – (PR2) – M] 3 4

Phosphide [M– (PR2) –M] 3 4

Alkoxide [M – (OR) – M] 3 4

* Sometimes counted as a four-electrons donor if it functions as a  donor.

Table 3.2: Details of some common ligands found in organometallic

compounds
Ligand Formal charge Electrons donated
H -1 2
F, Cl, Br, I -1 2
CN -1 2
-F, Cl, etc. -1 4
CO 0 2
-CO 0 2
PR3, PX3 0 2
CH3, C2H5, etc. -1 2
-CH3 -1 2
NO 0 2
5 -
 -[C5H5] -1 6
6
 -C6H6 0 6

SAQ 1
i) Identify the 3d metal in M2(CO)9 assuming it obeys 18 electron rule.
ii) Find the number of metal-metal bonds in Fe3(CO)12 and Co4(CO)12
iii) Find the charge of the complex [Fe(CO)4]x-

3.3 PREPARATION - DIRECT COMBINATION,

REDUCTIVE CARBONYLATION
In this section you will study the preparation of metal carbonyls by various
method and we will use T for temperature and P for pressure.
Preparation of Carbonyls
The known carbonyl of the 3d series are given in Table 3.3:
Table 3.3: Binary carbonyls of the 3d series

V(CO)6 Cr(CO)6 Mn2(CO)10 Fe(CO)5 Ni(CO)4

Fe2(CO)9 Co2(CO)8

Fe3(CO)12
Co4(CO)12

The two general methods of preparation of simple carbonyls are: 41

Block 1 Compounds of 3d Metals

(i) Direct reaction of metal with CO. This is possible for Fe, Ni and Co and
are given below.

200 ο C
   
Fe  5CO 100 atm P Fe(CO) 5 … (3.1)

room T
Ni  4CO    Ni(CO)4 … (3.2)
1atm P

200ο C
2Co  8CO    Co2 (CO)8 … (3.3)
100 atm P

The extreme ease of thermal decomposition of Ni(CO)4 is the basis of

Mond’s process for purification of Ni.

(ii) Reductive Carbonylation

Here, reduction of a metal salt takes place in presence of a reducing

agent and are given in the equations 3.4 to 3.9. The reducing agents
may be Mg, Ag, Cu, Na, LiAlH4 and even H2.
250ο C
2MnI2  10 CO  2Mg   Mn CO  2Mg I2
(

)
210 atmP 2 10 … (3.4)
(in diethyl ether)
200 ο C
diglyme is diethylene 2 CoS  8 CO  4 Cu     Co (CO)  2Cu S … (3.5)
200 atm P 2 8 2
glycol dimethyl ether.

200 ο C
FeS  5 CO  2 Cu    Fe (CO)  Cu S … (3.6)
200 atm P 5 2

120 o - 200 o C
2CoCO 3  8 CO  2 H 2 Co 2 (CO) 8  2H 2 O  2CO 2
250 - 300 atm P
… (3.7)

100 ο C
VCl 3  6 CO  3 Na    V (CO)  3NaCl
150 atm P 6

in diglyme Acidificat ion by H3 PO 4

… (3.8)
(

A synthetic method for making carbonyls from metal salts involves

reduction of an acetate hydrate by H2 in presence of CO and sufficient
acetic anhydride to convert water of hydration to acetic acid.
2 Co(CH COO)2 .4H2O  8(CH3CO) O  8 CO  2H  Co (CO)8  2CH3COOH
3 2 2 2

… (3.9)

(iii) Some carbonyls may be obtained from other carbonyls

The preparation of mononuclear carbonyls of molybdenum and

42 tungesten from iron pentacarbonyl is shown in Eq. 3.10.
Unit 3 Metal Carbonyl Compounds-I

100o C
MoCl6 /WCl 6  3Fe CO)5    Mo(CO)6 /W(CO)6  3FeCl2  9CO

(
… (3.10)

The carbonyl group in iron pentacarbonyl is very easily replaced by

The reaction in Eq.
chloride and thus different metal carbonyls may be obtained. Of course,
3.11 may take place
the yield is not very good, but increasing the pressure may improve the in two steps:
yield.
M(CO)5  M(CO)4 +
Methods of preparation of polynuclear carbonyls depend on the CO
particular metal. Eq. 3.11 gives the method of photolysis (irradiation with M(CO)4 + M(CO)5 
ultraviolet (UV) light) of the lower metal carbonyl Fe(CO)5 in glacial M2(CO)9
acetic acid whereby the higher metal carbonyl Fe2(CO)9 is obtained. M may be Fe or Os.

h
2Fe CO)5 Fe2 CO)9  CO … (3.11)
(

Photolysis of Os(CO)5 with UV light gives Os3(CO)12

h
3Os CO)5  Os 3 (CO)12  3CO … (3.12)
(

Heteronuclear carbonyls may be synthesised by methods as depicted in

Eq. 3.13 and 3.14. In Eq. 3.13 an anionic metal carbonyl reacts with a
metal carbonyl halide of a different metal and forms a heteronuclear
metal carbonyl incorporating both the metals.

Na[Co(CO)4 ]  Mn(CO)5 Br 

THF
 
 (CO)4 Co Mn(CO)5  NaBr … (3.13)

Eq. 3.14 show the formation of heteronuclear metal carbonyl by heating

a mixture of two metal carbonyls in the appropriate temperature whereby
there is loss of carbon monoxide.

110 ο C
3Fe (CO)5  Ru3 (CO)12    FeRu2 (CO)12  Fe2 Ru(CO)12  3CO

…(3.14)

SAQ 2
(i) Give the reaction for the photolysis of osmium pentacarbonyl.
(ii) Give two examples of preparation of metal carbonyls by reductive
carbonylation.

3.4 STRUCTURE (BASED ON VALENCE BOND

APPROACH) AND PROPERTIES
In this section you are going to study the structure of metal carbonyls based
on valence bond approach. Look at Fig. 3.1, where the valence bond
representations of CO and the MCO fragment are given.
:C O:
:
: :

M C O

Fig. 3.1: Valence bond representations of CO and the MCO fragment. 43

Block 1 Compounds of 3d Metals

The valence bond theory involves the concept of hybridization. The carbon
and oxygen atoms in CO are sp hybridized with the following electronic
configurations;

C (ground) state = 1s 2 , 2s 2 , 2 p1x , 2 p1y , 2 p z0

C (hybridized state) = 1s 2 , ( sp x ) 2 , ( sp x )1, 2 p 1y , 2 p z0

O (ground state) = 1s 2 , 2s 2 , 2 p1x , 2 p1y , 2 p z2

O (hybridized state) = 1s 2 , ( sp x ) 2 , ( sp x )1, 2 p 1y , 2 p z2

The  bond is formed from the overlap of one half-filled spx-hybridized orbital
of carbon atom and half-filled spx-hybridized orbital of the oxygen atom, while
spx-hybridized lone pairs on both atoms remains non-bonding in nature. As
shown in Fig.3.2, apart from this, the sidewise overlap of the orbitals which are
namely the half filled 2py orbitals, and the dative or coordinative interaction of
fully filled 2pz orbital of oxygen with empty 2pz orbitals of carbon result in two 
bonds between.
1
2py1 2py
1 2
2pz 2pz

2
spx2 spx1 spx1 spx

Carbon  spx2 , sp1x , sp1y , 2 p z0 Oxygen  spx2 , sp1x , 2 p 1y , 2 p z2

Fig. 3.2: Orbitals of C and O atoms.

Hence according to this model, the bonding within the CO molecule can be
described as shown in Fig.3.3 below:

Fig. 3.3: Bonding within the CO molecule

Now, let us look at the metal-carbonyls where the central metal atom or ion
furnishes the required number of empty hybrid orbitals to give the suitable
orientation required to accept the electron pair from surrounding ligands. For
example, in [Cr(CO)6] the chromium atom undergoes a d2sp3 hybridization and
furnishes six empty hybrid orbital of equivalent shapes and the same energy.

We start with the simplest carbonyls, that is the monomeric carbons. They
have symmetrical structures with linear M-C-O links. In all the structures the
44 CO ligands similar to the electron-pair in the VSEPR theory (BCHCT-131,
Unit 3 Metal Carbonyl Compounds-I

Unit-7) take the most distance positions. You can confirm the structures by
various spectroscopic techniques.

VSEPRT (Valence Shell Electron Pair Theory) predicts electrons which are
confirmed by X-ray diffraction:

Ni(CO)4 (Nickel tetracarbonyl) has the tetrahedral shape. It has linear Ni-C-O
bonds, with the bond length of Ni-C equals to 150 pm, bond length of C-O
equals to 115 pm (slightly longer than C-O in CO=112.8 pm). The tetrahedral
shape is due to sp3 hybridized nickel. The compound is diamagnetic with all
the electrons being paired. The details of the structure of Ni(CO)4 based on the
valence bond approach is shown in Table 3.4.

Table 3.4: Structure of Ni(CO)4 based on Valence Bond approach

Ni atom 3d 4s 4p

⇅ ⇅ ⇅ ↑ ↑ ⇅

3d 4s 4p

⇅ ⇅ ⇅ ⇅ ⇅

Fig. 3.4: Structure of

Rearrangement
Ni(CO)4
3d 4s 4p

Ni(CO)4 ⇅ ⇅ ⇅ ⇅ ⇅    

3
sp

 denotes electron pair from CO

The empty sp3 hybrid orbitals on Ni overlaps with filled orbital of CO forming
Ni-CO  bond as shown in Fig. 3.5.

Fig. 3.5: Orbital overlap in Ni-CO for  bond.

The negative charge on Ni which forms as a result of accumulation of electron

density of  bond formation is counterbalanced by formation of a back bond
by overlap of filled orbitals of nickel with vacant * molecular orbital of CO as
shown in Fig. 3.6.
vacant molecular orbital
 bond
  
+ + +

Ni + :C O: Ni :C O:

+    +
+

filled d orbitals

Fig. 3.6: Back Bonding of CO with Ni to form  bonds.

45
Block 1 Compounds of 3d Metals

Fe(CO)5 has TBP (trigonal bipyramidal) shape, the axial and equivalent bond
lengths are marginally different as shown by X-ray diffraction. The details of
the structure of Fe(CO)5 based on valence bond approach is given in
Table 3.5.

Table 3.5: Structure of Fe(CO)5 based on valence bond approach

Fe 3d 4s 4p

⇅ ↑ ↑ ↑ ↑ ⇅

Fe in Fe(CO)5 3d 4s 4p

⇅ ⇅ ⇅ ⇅

Rearrangement Fig. 3.7: Structure of

Fe(CO)5

3d 4s 4p

Fe(CO)5
⇅ ⇅ ⇅ ⇅     

3
dsp

 denotes electron pair from CO

Similarly it can be shown that Cr(CO)6 has octahedral structure. As CO

groups bring electrons in pairs it is clear that when the metal has odd number
of octahedral structure any mononuclear species will have an unpaired
electron.

Binuclear Carbonyls.

These are characterized by presence of M-M bond. the CO ligand can fulfill
three different structural functions and has three bonding modes each
recognized by a characterized CO stretching frequency and these are
compiled in Table 3.6.

Table 3.6: Details of CO stretching frequencies of metal carbonyls.

Free Terminal 1 2-Doubly 3-Triply

bridging bridging
(ketonic)

CO IR 2143 2120 - 1850 1850-1750 1730 - 1620

-1
(cm ) (for neutral
metal complexes)
46
Unit 3 Metal Carbonyl Compounds-I

This is a useful distiniction even though there are numerous borderline cases.
In carbonyl anions, where because of extensive back bonding, the stretching
frequency may fall below 1800 cm-1 although all carbonyl ligands are terminal.
Terminal carbonyl groups are most common in binuclear carbonyls.

Mn2(CO)10 has a structure composed of two staggered Mn(CO)5 units linked

by an Mn–Mn bond. The Mn-Mn bond distance is 279 pm. Each Mn atom is
linked to another Mn and 5 CO groups. There is no bridging carbonyl groups in
between the two Mn atoms. The compound is diamagnetic, each Mn atom has
coordination number 6 and is d2sp3 hybridised. The details of structure of
Mn2(CO)10 based on valence bond approach is given in Table 3.7.

Table 3.7: Structure of Mn2(CO)10 based on valence bond approach

Free Mn 3d 4s 4p
atom
↑ ↑ ↑ ↑ ↑ ⇅

One Mn 3d 4s 4p
atom in Structure as in Fig. 3.8.
Mn2(CO)10 ⇅ ⇅ ⇅     

Mn-Mn bond

3d 4s 4p

Another Mn
⇅ ⇅ ⇅     
atom
2 3
Mn2(CO)10 d sp

Fig. 3.8: Structure of Mn2(CO)10 molecule. This structure in its simplified form is
shown at the right hand side.

Fe2(CO)9 has both bridging terminal CO groups. the molecule is diamagnetic

and has short Fe-Fe distance indicating Fe-Fe bond ( bond) (246 pm). Each
Fe atom in linked to 3 bridging CO groups (>C=O) by a  bond and 3 terminal
CO groups coordinate bond. The bridging bonds are longer than terminal 47
Block 1 Compounds of 3d Metals

bonds and coordination number of Fe is 7. The details of structure of Fe2(CO)9

based on valence bond approach is given in Table 3.8.

Table 3.8: Structure of Fe2(CO)9 based on valence bond approach

Fe 3d 4s 4p

⇅ ↑ ↑ ↑ ↑ ⇅

Structure as in Fig.
3.9.
One Fe in 3d 4s 4p
Fe2(CO)9
⇅ ⇅      

Fe-Fe bond

3d 4s 4p

Another Fe
⇅ ⇅      
in Fe2(CO)9
2 3
d sp

Fig. 3.9: Structure of Fe2(CO)9

Co2(CO)8 is an orange-brown crystalline solid soluble in alcohol, ether and

CCl4. In solution the compound exists in two isomeric form, one having a
bridged structure (Fig. 3.10a) and the other a non-bridged structure (Fig.
3.10b). The two isomers are in equilibrium with each other and are
diamagnetic. X-ray structure of the crystal indicates a bridged structure in the
solid state.

(a) (b)
Fig. 3.10: Isomers of Co2(CO)8
48
Unit 3 Metal Carbonyl Compounds-I

The total electrons can be counted in both structures as shown below:

- -
Co 9e Co 9e

31CO 6e
-
41CO 8e
-

22CO 2e
-
Co-Co 8e
-

- -
1 Co-Co 1e Total Number of electrons 18 e
-
Total Number of electrons 18 e

The bridged structure Fig. 3.10a has 2 bridging CO groups; 3 terminal CO

groups and Co-Co bond. Each Co atom in linked to another Co, 3 terminal and
2 bridging CO groups giving a coordination number of 6 indicating d2sp3
hybridization. The details of these are given in Fig. 3.10 and Table 3.9.

Table 3.9: Structure of Co2(CO)8 based on valence bond approach

Free Co 3d 4s 4p

⇅ ⇅ ↑ ↑ ↑ ⇅

One Co in 3d 4s 4p
Co2(CO)8
⇅ ⇅ ⇅ ⇅ ↑    

Co– Co bond

3d 4s 4p

Another
⇅ ⇅ ⇅ ⇅    
Co in
2 3
Co2(CO)8 d sp

3 vacant d2sp3 hybrid orbitals on each Co atom accept a lone pair of electrons
donated by terminal CO groups forming 3 Co-Co bonds. Six such bonds are
formed. One of the singly filled d2sp3 hybrid orbitals on one Co atom combines
with another such orbital on another Co atom forming Co-Co bond. The
remaining two singly filled hybrid orbitals on each Co accept one electron from
bridging carbonyl groups. The non-bridged structure has one Co-Co bond and
eight terminal carbonyl groups.

So in this section we have discussed the structures of various metal carbonyls

and their relevant properties. Before going to the next section, please try the
following SAQ.

SAQ 3
(i) Give the structure with valence bond approach for Fe(CO)5.
(ii) How can you predict the number of metal-metal bonds in the isomers of
Co2(CO)8 assuming that it obeys 18 electron rule?
49
Block 1 Compounds of 3d Metals

3.5 PROPERTIES OF MONONUCLEAR AND

POLYNUCLEAR CARBONYL OF 3d METALS
This section will introduce you to the different properties of mononuclear and
polynuclear carbonyls of 3d metals. Let us first discuss the physical properties.
With the exception of mononuclear carbonyls of the iron group and Ni(CO)4, all
known carbonyls are solids. Apart from V(CO)6 which is black green in colour,
the mononuclear carbonyls are colourless and polynuclear carbonyls are
coloured, where the colour becomes darker with increase in number of metal
atoms. Fe(CO)5 is colourless (in some cases pale yellow) liquid, Fe2(CO)9
forms golden yellow plates and Fe3(CO)12 is very dark greenish black. Due to
their covalent nature they are insoluble in water but soluble in organic
solvents, like CCl4. Apart from V(CO)6 they are all diamagnetic.

Mononuclear metal carbonyl compounds take highly symmetric polyhedral

coordination structures. Hexa-coordinate chromium, molybdenum, and
tungsten hexacarbonyl, M(CO)6, assume a regular octahedral,
penta-coordinate pentacarbonyliron, Fe(CO)5, a triangular bipyramid, and
tetracarbonylnickel, Ni(CO)4, a regular tetrahedron coordination structure. The
carbon atoms of carbonyl ligands coordinate to the metal, and the carbonyl
moieties are oriented along the direction of the metal-carbon axis. Binuclear
metal carbonyl Mn2(CO)10 has an Mn-Mn bond joining two square pyramidal
Mn(CO)5 parts (as shown in Fig. 3.8). In Fe2(CO)9, two Fe(CO)3 sub-units are
bridged by three carbonyl ligands (as shown in Fig. 3.9), and in Co2(CO)8, two
Co(CO)3 sub-units are connected by both three CO bridges and a Co-Co bond
(as shown in Fig. 3.10).

There are a number of cluster metal carbonyl compounds with metal-metal

bonds joining three or more metals, and terminal CO, μ-CO (a bridge between
two metals), and μ3-CO (a bridge capping three metals) are coordinated to the
metal frames. Many cluster carbonyls are formed by a pyrolysis reaction of
mononuclear or binuclear carbonyl compounds. Typical metal carbonyl
compounds and their properties are shown in Table 3.10.

Table 3.10 : Metal carbonyl compounds and their properties

5 6 7 8 9

4 V(CO)6 Black Cr(CO)6 Mn2(CO)10 Fe(CO)5 Co2(CO)8

o
solid d.70 C White solid d. Yellow solid Yellow liquid Red solid
o o o o
90 C mp 154 C bp 103 C mp 51 C

5 Mo(CO)6 Tc2(CO)10 Ru3(CO)12 Rh6(CO)16

White solid White solid Orange solid Black solid
o o o
sublime mp 160 C d.150 C d.220 C

6 W(CO)6 Re2(CO)10 Os3(CO)12 Ir4(CO)12

White solid White solid Orange solid Yellow solid
o o o
sublime mp 177 C mp 221 C d.220 C

50 d = decomposition temperature; mp = melting point; bp = boiling point

Unit 3 Metal Carbonyl Compounds-I

Next, you are going to learn about the chemical properties of metal carbonyls.

Reaction of carbonyls

1. Fe(CO)5 when heated with alkali followed by oxidation with MnO2 gives
Fe3(CO)12

Fe CO  2OH  [HFe ( CO 4 ]   HCO 3 … (3.15)

(

)
5

3[HFe(CO) 4 ]  + 3MnO 2  Fe 3 (CO)12 + 3 OH + 3MnO … (3.16)

2. The most important reaction is formation of carbonylate anion by

addition of alkali or reduction as shown in Eq. 3.17 to 3.22. If you look
carefully in Eq. 3.17 you will see that the reaction of sodium hydroxide
with a metal carbonyl is basically a nucleophilic attack by a hydroxide ion
on the carbonyl group and thereby it gives a metal carboxylic acid
complex, which further reacts with sodium hydroxide to form a hydrido
anion.

Fe(CO)5  3NaOH  Na[HFe(CO)4 ]  Na 2CO3  H2O … (3.17)

NH 3
Fe(CO)5  2Na  Na 2 [Fe(CO)4 ]  CO … (3.18)

NH3
Fe2 (CO)9  4Na    2Na2 [Fe(CO)4 ]  CO … (3.19)

NH3
Co2 (CO)8  2Na    2Na[Co(CO)4 ] … (3.20)

NH3
Cr(CO) 6  2Na  
 Na 2 [Cr(CO) 5 ]  CO … (3.21)

NH3
Fe3 (CO)12  3Na    3Na[Fe(CO)4 ] … (3.22)

3. Formation of carbonyl hydrides takes place by reaction of metal

carbonyls with H2 is shown in Eq. 3.23 to Eq. 3.24.
200C
Mn 2 (CO)10  H2    2[HMn(CO)5 ] … (3.23)

165C
Co 2 ( CO )8  H2 2[HCo(CO) 4 ] … (3.24)
200 atm

4. Formation of carbonyl halides takes place by reaction of metal carbonyls

with halogen. You will find the common reaction of metal carbonyls with
halogens in Eq. 3.25 to 3.28.
Fe ( CO ) 5  X 2  Fe(CO) 4 X 2  CO … (3.25)

In Eq. 3.26, the halogen reacts to form lower carbonyl by causing

cleavage in the metal-metal bond.

51
Block 1 Compounds of 3d Metals

40C
Mn 2 (CO)10  Br2   2Mn(CO) 5 Br … (3.26)

Co2(CO)8 and Ni(CO)4 decompose in presence of halogens forming

halides and is shown in Eq. 3.27 and Eq. 3.28.

Co2 (CO)8  2X2  2CoX2  8CO … (3.27)

Ni(CO) 4  Br2  NiBr2  4CO … (3.28)

5. Displacement of CO by other ligands which are actually substitution

reactions as shown in Eq. 3.29 to 3.33.

Ni(CO)4  2PF3  Ni(CO)2 (PF3 )2  2CO … (3.29)

Ni(CO) 4  RCN  Ni(CNR) 4  4CO … (3.30)

Fe(CO)5  PPh 3  Fe(CO)4 (PPh 3 )  CO … (3.31)

Cr(CO)6  C 6H6  Cr(CO)3 (C6H6 )  3CO … (3.32)

Mn2 (CO)10  PR 3  2 Mn (CO)4 (PR3 )  2CO … (3.33)

6. Formation of nitrosyl with NO take place as shown in Eq. 3.34 to 3.36.

Fe(CO)5  2NO  2 Fe (CO)2 (NO)2  3CO … (3.34)

Fe3 (CO)12  6NO  3 Fe (CO)2 (NO)2  6CO … (3.35)

Co 2 (CO)8  2NO  2 Co(CO)3 (NO)  2CO … (3.36)

7. Action of heat – This varies from case to case as shown in Eq. 3.37 to
3.42.
200 o C
Fe(CO) 5     Fe  5 CO … (3.37)

70 o C
3Fe 2 (CO) 9   3Fe(CO)  Fe (CO) … (3.38)
Toluene 5 3 12

50 o C
3Fe 2 (CO) 9   2Fe 3 (CO)12  3CO … (3.39)

140o C
Fe3 (CO)12    3Fe  12 CO … (3.40)

50o C
2Co 2 (CO)8   Co 4 (CO)12  4CO … (3.41)

180o C
Ni(CO)4    Ni  4CO … (3.42)

SAQ 4
(i) Give the equation for formation of carbonyl hydrides with hydrogen for a
carbonyl of cobalt.

52
Unit 3 Metal Carbonyl Compounds-I

(ii) How can formation of nitrosyl complexes be formed from carbonyl

complexes? Give any one suitable equation to show this.

3.6 SUMMARY
In this unit discussions about the EAN Rule and 18 Electron Rule as applied to
carbonyls were done at first. Next the preparation of metal carbonyls through
direct combination and reductive carbonylation were also taken up. The
structure of metal carbonyls based on Valence Bond approach and properties
were then discussed in detail. Lastly the properties of mononuclear and
polynuclear carbonyl of 3d metals have been discussed. In the next unit you
are going to learn more about the metal carbonyls.

3.7 TERMINAL QUESTION

1. Give the method of preparation of Fe(CO)5 from iron powder.
2. Show that Fe3(CO)12 obeys 18 electron rule.
3. Explain the structure of Fe2(CO)9 based on valence bond approach.
4. What is the carbonylate anion? Give any two reactions where its
formation takes place from metal carbonyls.

3.8 ANSWERS
Self Assessment Questions
1. i) Let number of electrons on M = n  2M = 2n electrons

M-M bond = 2 electrons

9 CO = 18 electrons

2n + 2 + 18 = 36 2n = 16  n = 8

As metal is in zero oxidation state it is Fe.

ii) Fe3 (CO)12 Let number of Fe-Fe bonds = x; each bond involve 2
electrons from Fe-Fe bond = 2x
-
3 Fe 24 e
-
12 CO 24 e
electrons from Fe-Fe bonds 2x
Total number electrons 24 + 24 + 2x = 54
2x = 6  x = 3

For Co4(CO)12 , similarly we can say,

-
4 Co (4 × 9) e
-
12 CO 24 e
53
Block 1 Compounds of 3d Metals

electrons from Co-Co 2x

bonds

Total number electrons 36 + 24 + 2x = 72

2x = 12  x = 6

iii) Fe has 8 electrons. So we see,

8 + (2  4) + x = 18  x = 2
2-
= Charge is -2, [Fe(CO)4]

2. i) Eq. 3.12

ii) Reductive carbonylation involves the reduction of a metal salt in

presence of a reducing agent. The reducing agents may be Mg, Ag
etc. Eq. 3.4 to 3.9 are examples. (any two examples with equations
may be given)

3. i) Fe(CO)5 is TBP (details as in Table 3.5)

ii) Co2(CO)8 has one metal-metal bond assuming it obeys 18 electron

rule (calculations given below Fig. 3.10.)

4. i) Eq. 3.24

ii) Any equation, from Eq. 3.34 to Eq. 3.36

Terminal Questions

1. Eq. 3.1

2. Refer to Table 3.5. and extent it to Fe3(CO)12.

-
3 Fe 3x8 24 e
-
12 CO 12 x 2 24 e
Total electron count 48

So number of metal-metal bonds (Fe-Fe) must be  3x2=6

Total electron count 54 e-

Therefore 18 electron per Fe atom

3. Table 3.7

4. Carbonylate anion is the anion which has carbonyl (CO) in it. It is formed
as shown in Equations. 3.17 to 3.22.

54