B. Sc.

(Sem-III)
Sub: Inorganic Chemistry (US03CCHE21)
UNIT IV
METALLIC CARBONYLS AND METALLIC NITROSYLS
Introduction:
The electronic configuration of CO molecule shows that both carbon
and oxygen atoms have a lone pair of electrons. Carbon atom can donate its
electron pair to a transition metal atom to form OC→M coordinate bond.
Hence the compounds form by combination of CO molecules, with transition
metals are known as metallic carbonyls. Since the electrons supplied solely
by CO molecule in the formation of OC→M bond, metal atom in carbonyl has
zero oxidation state.

Carbonyls have been classified on the basis of the number of metal

atoms present in the carbonyl as under.

(i) Mononuclear (or monomeric) carbonyl:

Which is having only one metal atom per molecule and having type
M(CO)y. e.g. V(CO)6, Cr(CO)6 etc.

(ii) Polynuclear carbonyl:

Which contain two or more metal atoms per molecule having type Mx(CO)y.
however some authors call carbonyls containing two metal atoms are
called bridged carbonyl and which containing more than two metal atoms
are called polynuclear carbonyls which may be homonuclear e.g.
Fe3(CO)12 or heteronuclear e.g. MnCo(CO)9, MnRe(CO)10 etc.

GENERAL METHODS OF PREPARATION

Following are some of the general methods of preparation of metal
carbonyls.

(i) Direct Synthesis: Only Ni(CO)4 and Fe(CO)5 and Co2(CO)8 are normally
obtained by the action of CO on the finely divided metal at suitable
temperature and pressure.
o
200 C, 100 atm press.
Fe + 5CO ⎯⎯ ⎯⎯⎯⎯⎯⎯ ⎯→ Fe(CO) 5

Ni + 4CO ⎯R.T.,
⎯ ⎯100⎯atm
⎯⎯ press.
⎯⎯→ Ni(CO) 4
o
200 C, 100 atm press.
2Co + 8CO ⎯⎯ ⎯⎯⎯⎯⎯⎯ ⎯→ Co 2 CO) 8
(ii) By carbonylating metallic salts with CO in presence of reducing
agent:

Metallic carbonyls are obtained when salts like RuI3, CrCl3, VCl3, CoS,
Co(CO)3, CoI2 etc. are treated with CO in presence of suitable reducing
agent like Mg, Ag, Cu, Na, H2, AlLiH4 etc.
o
CrCl 3 + 5CO + LiAlH 4 ⎯115
⎯ ⎯C,⎯70⎯atm
⎯press.
⎯⎯→ Cr(CO) 6 + LiCl + AlCl 3

o
RuI 3 + 10CO + 6Ag ⎯175
⎯ ⎯C,⎯250
⎯atm
⎯⎯press.
⎯⎯→ 2Ru(CO) 5 + 6AgI
o
25 C, 210 atm press.
2 MnI 2 + 10CO + 2Mg ⎯⎯ ⎯ ⎯ ⎯ ⎯ ⎯⎯→ Mn 2 (CO) 5 + 2MgI 2
(in diethyl ether)

o
200 C, 200 atm press.
2CoS + 8CO + 4Cu ⎯⎯ ⎯⎯⎯⎯⎯⎯ ⎯→ Co 2 (CO) 8 + 2Cu 2S

o
200 C, 200 atm press.
2CoI 2 + 8CO + 4Cu ⎯⎯ ⎯⎯⎯⎯⎯⎯ ⎯→ Co 2 (CO) 8 + 4CuI

o
200 C, 200 atm press.
2FeI 2 + 5CO + 2Cu ⎯⎯ ⎯⎯⎯⎯⎯⎯ ⎯→ Fe(CO) 5 + Cu 2 I 2

o
2CoCO3 + 8CO + 2H 2 ⎯120
⎯⎯ -200 C, 250-300 atm press.
⎯⎯⎯⎯⎯⎯⎯⎯ ⎯→ Co 2 (CO) 8 + 2CO2 + 2H 2O

o
2Cr(acac) 3 + 12CO + 3Mg ⎯160
⎯ ⎯C,⎯300
⎯atm
⎯⎯press.
⎯⎯→ C3Mg(acac) 2 + 2Cr(CO) 6
(inpyridine)

MoCl 5 + 6CO + 5Na ⎯(in

⎯diglyme)
⎯⎯⎯→ Mo(CO) 6 + 5NaCl

Sometimes CO acts as a carbonylating and reducing agent as under.

o
250 C, 350 atm press.
OsO5 + 5CO ⎯⎯ ⎯⎯⎯⎯⎯⎯ ⎯→ Os(CO) 5 + 2O2

Re 2 O 7 + 10CO ⎯
⎯→ Re 2 (CO)10 + 7O2

V(CO)6 is prepared by the method represented by the following equation

o
VCl 3 + 6CO + Na ⎯100
⎯ ⎯C,
⎯150
⎯atm
⎯⎯press.
⎯⎯→ V(CO) 6 + 3NaCl
(indiglyme ) acidificat ion by H PO
3 4

(iii) Preparation of Mo(CO)6 and W(CO)6 from Fe(CO)5:

MoCl5 and WCl5 give the corresponding hexacarbonyls. These reactions

are characterized by low yield, which can be improved by using high
pressure.
 o
MoCl 6 + 3Fe(CO) 5 ⎯110
⎯⎯C,⎯ether
⎯⎯→ Mo(CO) 6 + 3FeCl 2 + 9CO
o
WCl 6 + 3Fe(CO) 5 ⎯110
⎯⎯C,⎯ether
⎯⎯→ W(CO) 6 + 3FeCl 2 + 9CO

(iv) Preparation of Fe2(CO)9, and Os2(CO)9 from Fe(CO)5:

When cool solution of Fe(CO)5 and Os(CO)5 in glacial CH3COOH is

irradiated with ultra-violet light, Fe2(CO)9, and Os2(CO)9 are obtained
respectively.

Fe(CO) 5 ⎯UV
⎯⎯ -light
⎯→ Fe 2 CO) 9 + CO

Os(CO) 5 ⎯UV
⎯⎯ -light
⎯→ Os 2 CO) 9 + CO

GENERAL PROPERTIES

Physical properties:
(i) Most carbonyls are volatile solids but Fe(CO)5, Ru(CO)5, Os(CO)5 and
Ni(CO)4 are liquids at ordinary temperature and quite inflammable.
(ii) Many of these decompose or melt at low temperature.
(iii) They are soluble in organic solvents. Ni(CO)4 is insoluble in water but
others react with it.
(iv) All carbonyls, except V(CO)6, are diamagnetic substances. Metals with odd
atomic number couple the odd electrons to form metal-metal bond.
Probably the steric factor prevents V(CO)6 from dimerization.
(v) All carbonyls are thermodynamically unstable with respect to oxidation in
air, but their rates vary widely. CO2(CO)8 reacts at ordinary temp. Fe2(CO)9
and Ni(CO)4 are also readily oxidized (their vapours forming explosive
mixtures with air); M(CO)6, M = Cr, MO, W react only when heated.

Chemical properties:
(i) Substitution reaction:

Some or all CO groups present in carbonyl can be replaced by

monodentate ligands like isocyanide (CNR), PR3, PCl3, py, CH3OH etc.
e.g.

Ni(CO)4 + 4CNR ⎯
⎯→ Ni(CNR) + 4CO

Ni(CO)4 + 4PCl3 ⎯
⎯→ Ni(PCl3) + 4CO

Fe(CO)5 + 2CNR ⎯
⎯→ Fe(CO)3(CNR)2 +2CO

Mn2(CO)10 + PR3 ⎯
⎯→ 2Mn(CO)4(PR3) + 2CO
 2Fe2(CO)12 +3py ⎯
⎯→ Fe3(CO)9(py)3 + 3Fe(CO)5

2Fe2(CO)12 +3CH3OH ⎯
⎯→ Fe3(CO)9(CH3OH)3 + 3Fe(CO)5

Bidentate ligands like diars, o-phen, NO2 etc. replace at two or more CO
group at a time. e.g.

Mo(CO)6 + diars ⎯
⎯→ Mo(CO)4(diars) + 2CO

Fe(CO)s + diars ⎯
⎯→ Fe(CO)3diars +2CO

Ni(CO)4 + o-phen ⎯
⎯→ Ni(CO)2(o-phen)2 + 2 CO

Ni(CO)4 + diars ⎯
⎯→ Ni(CO)2(diars) + 2 CO

Cr (CO)6 + 2diars ⎯
⎯→ Cr(CO)2(diars)2 + 4CO

Ni(CO)4 + 2NO2 ⎯
⎯→ Ni(NO2)2 + 4CO

(ii) Action of NaOH or Na metal:

Formation of carbonylate anion (reduction). Aqueous or alcoholic

solution of NaOH reacts with Fe(CO)5 to form carbonylate anion,
[HFe(CO)4]-

Fe(CO)5 + 3NaOH → Na + [H + Fe 2- (CO) 4 ]- + Na 2CO3 + H 2O

(Fe = 0)

H-atom in [H+Fe2-(CO)4]- ion is acidic which means that Fe-atom in this

ion is in -2 oxidation state.
Na-metal in liquid NH3 converts Fe2(CO)9, Co2(CO)8, Fe3(CO)12, Cr(CO)6,
Mn2(CO)10 etc. in to carbonylate anions and in these carbonyls are
reduced.
Fe 2 (CO) 9 + 4Na → 2 Na 2 + [Fe 2- (CO) 4 ]2- + CO
(Fe = 0)
Co 2 (CO) 8 + 2Na → 2 Na + [Co - (CO) 4 ]-
(Co = 0)

Fe 3 (CO)12 + 3Na → 3Na + [Fe - (CO) 4 ]-

(Fe = 0)

Cr(CO) 6 + 2Na → Na 2 + [Cr 2- (CO) 5 ]2- + CO

(Cr = 0)

Mn 2 (CO)10 + 2Na → 2 Na + [Mn - (CO) 5 ]-

(Mn = 0)
(iii) Carbonyl react with halogens to form carbonyl halides shown as under.

Fe(CO)5 + X2 ⎯
⎯→ Fe(CO)4X2 + CO

Mo(CO)6 + Cl2 ⎯
⎯→ Mo(CO)4Cl2 + 2CO

Mn2(CO)10 + X2 (X=Br, I) ⎯
⎯→ 2Mn(CO)5X

Co2(CO)8 and Ni(CO)4 both get decomposed into metallic halides and CO
when treated with halogens. e.g.

Co2(CO)8 + 2X2 ⎯
⎯→ 2CoX2 + 8CO

Ni(CO)4 + Br2 ⎯
⎯→ NiBr2 + 4CO

(iv) Action of NO:

Many carbonyl react with nitric oxide to form metal carbonyl nitrosyls. e.g
95o C
Fe(CO)5 + 2 NO ⎯⎯ ⎯ ⎯→ Fe(CO)2(NO)2 + 3CO

3Fe2(CO)9 +4NO ⎯
⎯→ 2Fe(CO)2(NO)2 +Fe2(CO)5 + Fe3(CO)12 + 6CO

85o C
Fe3(CO)12 + 6NO ⎯⎯ ⎯ ⎯→ 3Fe(CO)2(NO)2 + 6CO
40o C
Co2(CO)8 + 2NO ⎯⎯ ⎯ ⎯→ 3Co(CO)3(NO) + 2CO

Moist NO gives a blue coloured compound, Ni(NO)(OH) with Ni(CO)4while

dry NO gives a blue solution of the composition, Ni(NO)(NO2)

2Ni(CO)4 + 2NO + 2H2O ⎯

⎯→ 2Ni(NO)(OH) + 8CO + H2

Ni(CO)4 + 4NO ⎯
⎯→ Ni(NO)(NO2) + 4CO + N2O

(iv) Action of H2:

When Mn2(CO)10 and Co2(CO)8 react with H2, they are reduced to
carbonyl hydride, Mn(CO)5H and Co(CO)4H respectively.
Mn 2 (CO)10 + H 2 ⎯200
⎯⎯ atm. press.
⎯⎯⎯→ 2[Mn - (CO) 5 H + ]0

o
Co 2 (CO) 8 + H 2 ⎯165
⎯ ⎯C,⎯200
⎯atm.
⎯⎯ press.
⎯⎯→ 2[Co - (CO) 4 H + ]0

(v) Action of Heat:

Different carbonyls give different product when heated shown below.
 o
Fe(CO) 5 ⎯250
⎯⎯ C
⎯ → Fe + 5CO
o
70 C, cool
3Fe 2 (CO) 9 ⎯⎯⎯⎯⎯→ 3Fe(CO) 5 + Fe 3 (CO)12
(in toluene)

o
140 C, cool
Fe 3 (CO)12 ⎯⎯⎯⎯⎯
⎯→ 3Fe + 12CO

o
2Co 2 (CO) 8 ⎯50
⎯⎯ C, inert atmosphere
⎯ ⎯ ⎯ ⎯ ⎯⎯→ Co 4 (CO)12 + 4CO

o
180 C
Ni(CO) ⎯⎯ ⎯
⎯→ Ni + 4CO
4

o
50 C
3Fe 2 (CO) 9 ⎯⎯⎯
⎯→ 2Fe 3 (CO)12 + 3CO
(in toluene)

Structure and nature of M-CO bonding in carbonyls:

This can be explained by considering the formation of σ-bonds and π-
bonds. The lone paired of electron on carbon atom would expect to form
strong σ-dative bond due to electron density remain to the carbon nucleus.
Formation of dative σ-bonds:
It is form as a result of overlapping of empty hybrid orbital of metal
atom with the filled hybrid orbital on carbon atom of CO molecule and form
M←CO σ-bonds. i.e. formation of Ni←CO σ-bonds in Ni(CO)4 takes place by
the overlap between empty sp3 hybrid orbital on Ni and filled sp orbital on
carbon atom of CO molecule. Other three Ni←CO bonds are formed in the
same manner.

In the type of M(CO)5 and M(CO)6 carbonyls dsp3 and d2sp3 hybrid
orbital are used for M←CO σ-bonds. In this bond formation, metal atom acts
as electron acceptor, while CO acts as electron donor.
Formation of dative π-bonds:
This bond is formed as a result of overlapping of filled dπ orbitals or
hybrid pπ orbitals of metal atom with low-lying empty pπ-orbitals on CO
molecule. i.e. M ⎯⎯→
π CO
i.e. Ni→CO π-bond in Ni(CO)4 form by overlap between filled dz2 or dx2-y2 on
Ni atom and empty π* molecular orbital on CO molecule.
In M(CO)6 type molecule, since dz2 or dx2-y2 orbital are used for d2sp3
hybridization, M→CO π-bond form by overlapping with filled dxy, dyz or dxz
orbital of M with empty π* molecular orbital on CO molecule. Out of six CO,
three are linked by M←CO σ-bond and remaining three is linked by M←CO
and M→CO π-bond.
The main evidence for multiple nature of M-CO bonds comes from bond
lengths and vibrational spectra. As M-CO donation increases, the M-C bond
becomes stronger and the C=O bond becomes weaker. Thus, the multiple
bonding would result in shorter M-C bonds and longer C-O bonds as
compared M-C single bonds and C=O triple bonds respectively. The C-O bond
lengths are rather insensitive to bond order, the M-C bonds show appreciable
shortening consistent with π-bonding concept. Some M-C distances are:

V(CO)6: 2.00 ; Mo(CO)6: 2.06; Cr(CO)6: 1.92 ; W(CO)6: 2.07

Fe(CO)5: 1.80 (axial), 1.85 (trig – equatorial); Ni(CO)4: 1.84

Bridging CO groups:
In addition to linear M-C-O groups, in some binuclear and polynuclear
carbonyls the CO group is known to fulfill bridging functions.

In a terminal M-C-O group the CO donates 2 electrons to an empty

metal orbital, while in bridging M(CO) M group the M-C bond is formed by
sharing of one metal electron and one carbon electron.

Effective atomic number rule (EAN):

In the formation of M←CO bond, CO molecule electron pair to the

metal atom. Thus, the metal atom is said to be have zero valency. The rule is
state that “After CO groups donated a certain number of electron pairs
to the zero valent metal atom through OC→M σ-bonding, the total
number of electrons on metal atom including those gained from CO
molecule becomes equal to the atomic number of the next inert gas”.
EAN = z + 2Y = G
Where, z = total electrons of metal atom
Y = total electron donated by CO groups
G = Effective atomic number of next inert gas
In carbonyls, CO can donate two electrons at a time, so only even
number of transition metal can achieve the effective atomic number of next
inert gas. e.g. for Cr(CO)6,
EAN = z + 2Y = 24 + (2x6) = 36 = Ar

1) Mononuclear carbonyl having transition metal atom in even atomic

number in zero oxidation state.

EAN of some mononuclear carbonyls are calculate in the following table

Metal No. of ēs on the No. of ēs EAN of the metal atom

carbonyl central metal donated by CO in carbonyl
atom = At. No.of molecule = 2Y = z + 2Y
metal = z

Cr(CO)6 24 6 x 2 = 12 24 + 12 = 36[Kr]

Mo(CO)6 42 6 x 2 = 12 42 + 12 = 54 [Xe]

W(CO)6 74 6 x 2 = 12 74 + 12 = 86 [Rn]

Fe(CO)5 26 5 x 2 = 10 26 + 10 = 36 [Kr]

Ru(CO)5 44 5 x 2 = 10 44 + 10 = 54 [Xe]

Os(CO)5 76 5 x 2 = 10 76 + 10 = 86 [Rn]

Ni(CO)4 28 4x2=8 28 + 8 = 36 [Kr]

2) Mononuclear carbonyl having transition metal atom in odd atomic

number i.e. V(CO)6 and hypothetical carbonyls Mn(CO)6 and Co(CO)4 etc.
These carbonyls do not obey EAN rule because metal atom does not
achieve next inert gas configuration.
V(CO)6: 23 + (2 x 6) = 35
 Mn(CO)5: 25 + (2 x 5) = 35

Co(CO)4: 27 + (2 x 4) = 35
3) Polynuclear carbonyl: The polynuclear carbonyls obey EAN rule. Two ēs
each of M-M bond present in these carbonyls are included in calculating
the ēs per metal atom.
Mn2(CO)10: ēs from two Mn = 25 x 2 = 50
ēs from ten CO = 2 x 10 = 20
ēs from one Mn-Mn bond = 2
hence EAN of each Mn atom = 72/2 = 36 [Kr]

Fe3(CO)12: ēs from three Fe = 26 x 3 = 72

ēs from twelve CO = 2 x 12 = 24
ēs from three Fe-Fe bonds = 6
hence EAN of each Fe atom = 108/3 = 36 [Kr]

18-electron rule as applied to metallic carbonyls:

The formation of mononuclear carbonyls by transition elements with even

atomic number can also be explained on the basis of 18-electron rule as
shown below.

For mononuclear carbonyls, M(CO)y

i.e. Ni(CO)4: No. of the valence electrons of metal atom = 10
No. of the electrons donated by CO groups = 8
Total number of electrons on the metal atom = 18

Fe (CO)5: No. of the valence electrons of metal atom = 8

No. of the electrons donated by CO groups = 10
Total number of electrons on the metal atom = 18

Cr(CO)6: No. of the valence electrons of metal atom = 6

No. of the electrons donated by CO groups = 12
Total number of electrons on the metal atom = 18

The formation binuclear carbonyls having metal atom with odd atomic
number can also be explained on the basis of 18-electron rule as shown below
for Co2(CO)8 and Mn2(CO)10 carbonyls.
Co2(CO)8: No. of the valence electrons of two Co atoms = 2 x 9 = 18
No. of the electrons donated by CO groups = 2 x 8 = 16
No. of electron for Co-Co bond = 1 x 2 = 2
Total number of electrons on two Co atoms = 36
Therefore, electrons on one Co atom = 36/2 = 18
 Mn2(CO)10: No. of the valence electrons of two Mn atoms = 2 x 7 = 14
No. of the electrons donated by CO groups = 2 x 10 = 20
No. of electron for Mn-Mn bond = 1 x 2 = 2
Total number of electrons on two Mn atoms = 36
Therefore, electrons on one Mn atom = 36/2 = 18

Here, it may be noted that though Fe has an even atomic number (i.e. 26), the
formation of its binuclear carbonyl, Fe2(CO)9 can also accounted for by the 18-
electron rule as under.
Fe2(CO)9: No. of the valence electrons of two Fe atoms = 2 x 8 = 16
No. of the electrons donated by CO groups = 2 x 9 = 18
No. of electron for Fe-Fe bond = 1 x 2 = 2
Total number of electrons on two Fe atoms = 36
Therefore, electrons on one Fe atom = 36/2 = 18

SOME INDIVIDUAL CARBONYLS

1. Nickel tetra carbonyl, Ni(CO)4:
Preparation:
(i) Direct synthesis: CO is passed over reduced Ni at 60 oC
o
Ni + 4CO ⎯60
⎯⎯ C
→ Ni(CO) 4

(ii) From NiI2: NiI2 is heated with Co in the presence of a halogen receptor.

NiI 2 + 4CO ⎯
⎯→ Ni(CO) 4 + I 2

(iii) From nickel salt: Passing CO through alkaline suspension of NiS or

Ni(CN)2

NiS + 4CO ⎯
⎯→ Ni(CO) 4 + S

Ni(CN) 2 + 4CO ⎯
⎯→ Ni(CO) 4 + C 2 N 2

Properties:

(i) Colorless liquid having m.p. -25o C and b.p. 43 oC, insoluble in water but
dissolves in organic solvents. It decomposes at 180 – 200 oC.

(ii) Action of H2SO4: conc. H2SO4 reacts with detonation

Ni(CO)4 + H2SO4 ⎯
⎯→ NiSO4 + H2 + 4CO

(iii) Action of NO: With moist NO it gives intense blue compound Ni(NO)(OH).

2Ni(CO)4 + 2NO + 2H2O ⎯

⎯→ 2Ni(NO)(OH)+ 8OH + H2
(iv) Substitution reactions: see “general properties of carbonyls”.

(v) Action of heat: see “general properties of carbonyls”.

(vi) Action of Halogen: see “general properties of carbonyls”.

(vii) Action of gaseous HCl Gaseous HCl decomposes the solution of Ni(CO)4,
evolving H2 and CO

Ni(CO)4 + 2HCl(g) ⎯
⎯→ NiCl2 +H2 + 4CO

Uses:

(i) Since Ni(CO)4, on heating, is decomposed to metallic nickel, it is use in the

production of nickel by Mond’s process.

(ii) It is also used in gas planting and as a catalyst.

Structure:

The vapour density and freezing point of its solution in C6H6 indicates
that it has formula Ni(CO)4. Electron diffraction studies in vapour state and
X-rays studies in the solid state shows the tetrahedral structure. Ni-C bond
length is1.5 Ǻ.

Tetrahedral shape of Ni(CO)4 results from sp3 hybridization of Ni-atom.

Since Ni(CO)4 molecule is diamagnetic, all the ten electrons present in the
valence shell of Ni atom (Ni = 3d8 4s2) gets paired in 3d orbitals. Thus the
valence shell configuration of Ni atom in Ni(CO)4 molecule becomes 3d10 4s0.
OC→Ni bond results by the overlap between the empty sp3 hybrid orbital on
Ni atom and doubly filled sp orbital on C-atom in CO molecule as shown
below.
2. Iron pentacarbonyl, Fe(CO)5:
Preparation:
(i) Action of CO on iron powder at 200 0C and 100 atmosphere pressure.
200 o C, 100 atm.
Fe + 5CO ⎯⎯ ⎯ ⎯ ⎯ ⎯⎯→ Fe(CO) 5
(ii) By carbonylating FeI2 or FeS with CO in presence of Cu-metal which acts
as a reducing agent.
200 o C, 200 atm.
2FeS + 10CO + 2Cu ⎯⎯ ⎯ ⎯ ⎯ ⎯⎯→ Fe(CO) 5 + Cu 2S
Properties:
(i) Fe(CO)5 is pale yellow liquid ; b.p. 103 oC, soluble in methyl alcohol, ether,
acetone and C6H6. It is insoluble in water.
(ii) Decomposition: At 250 oC, it decomposes to give pure Fe.
250 o C
2Fe(CO)5 ⎯⎯ ⎯⎯→ Fe + 5CO
(iii) Action of ultra-violet light: When cooled solution of Fe(CO)5 in glacial
CH3COOH is treated with ultra-violet light, Fe2(CO)9 is formed.
UV - light
2Fe(CO)5 ⎯⎯⎯⎯
⎯→ Fe 2 (CO) 9 + CO
(iv) Hydrolysis: It is hydrolyzed with water and acids.
Fe(CO) 5 + H 2SO 4 ⎯
⎯→ FeSO 4 + 5CO + H 2
(v) Action of alkali: When heated with aqueous or alcoholic solution of NaOH,
carbonylate anion, [Fe2(CO)4H+]- is formed. The hydrogen atom in this
anion is acidic which means that Fe is in -2 oxidation state.
⎯→ Na + [Fe 2 - (CO) 4 H + ]- + Na 2 CO 3 + H 2 O
Fe(CO) 5 + 3NaOH ⎯
( Fe = 0) ( Fe = −2)
(vi) Action of NH3: With NH3 it gives Fe(CO)4H2 and carbamic acid, NH2COOH.
Fe(CO)5 + H2O + NH3 ⎯ ⎯→ Fe(CO)4H2 + NH2COOH
(vi) Reaction with halogen: It react with halogens in non-aqueous solvent to
form the stable tetra carbonyl halides, Fe(CO)4X2.
Fe(CO)5 +X2 ⎯
⎯→ Fe(CO)4X2 + CO
Structure:
The vapour density and freezing point of its C6H6 solution studies
indicates it has formula Fe(CO)5. Electron diffraction studies in vapour state
and X-rays studies in the solid state shows that it has trigonal bipyramidal
structure. Three CO groups are in the equatorial position, while among two,
one is above the plane and other is below the plane, in the polar position.
There is dsp3 hybridization occurs between the orbitals of Fe atom. All
eight electrons of Fe atom paired in 3d orbital. Fe(CO)5 is diamagnetic. The
OC→Fe bond is formed by overlapping of empty dsp3 hybrid orbitals with
doubly filled sp hybrid orbital on C-atom in CO molecule as shown below.

3. Chromium hexacarbonyl, Cr(CO)6:

Preparation:

(i) By carbonylating CrCl3 with CO in presence of a reducing agent like lithium

aluminium hydride, LiAlH4.

CrCl3 + CO + LiAlH4 → Cr(CO)3 + LiCl + AlCl3

(ii) Br treating CrCl3 with CO in presence of C6H5MgBr (Job’s Grignard
reaction) under appropriate conditions. (i.e. By passing CO to 50 atm
pressure and at room temperature into a suspension of CrCl3 in either
which has been treated with C6H5MgBr at – 270C).

Properties:

(i) It is colourless, insoluble crystals which sublime without decomposition

and dissolve in either, CHCl3, CCl4, C6H6.

(ii) It is not attacked by air, bromine, cold aqueous alkalis. Dilute acids and
conc. HCL and H2SO4. It is decomposed by Cl2 and Conc. HNO3

(iii) It is decomposed by F2 at -75 oC to form CrF6.

(iv) Alkali metal in liquid ammonia reacts to give Na2[Cr(CO)5]

liq. NH
Cr(CO) 6 + 2 Na ⎯⎯ ⎯⎯
3
→ Na 2 + [Cr 2 - (CO) 5 ]2 - + CO
(Cr = 0)

(v) Some carbonyls present in the Cr(CO)6 can be replaced by pyridine (py)
toget a number of compounds.

py py py
Cr(CO) 6 ⎯⎯→ Cr(CO) 4 (py) 2 ⎯⎯→ Cr2 (CO) 9 ⎯⎯→ Cr(CO) 3 (py) 3
yellow brown yellow red bright red

Structure:

The electron diffraction studies indicate that it has octahedral. There is

d2sp3 hybridization occurs between the orbitals of Cr atom. All the six
electrons of Cr (3d5 4s1) paired in 3d orbitals. Cr(CO)6 is diamagnetic. The
OC→Cr bond is formed by overlapping of empty d2sp3 hybrid orbitals with
doubly filled sp hybrid orbital on C-atom in CO molecule as shown below.
4. Dimanganese decacarbonyl, Mn2(CO)10:
Preparation:
(i) By carbonylating MnI2 with CO in presence of Mg (in diethyl ether) which
acts as a reducing agent.
25 o C, 210 atm.
2MnI 2 + 10CO + 2Mg ⎯⎯⎯⎯⎯⎯
⎯→ Mn 2 (CO)10 + 2MgI 2
in diet hyl ether
(ii) By carbonylating MnCl2 with CO in presence of (C6H5)2CONa.

165 o C, 140 atm.

2MnCl 2 + 10CO + 4(C 6 H 5 ) 2 CONa ⎯⎯ ⎯ ⎯ ⎯ ⎯
⎯→ Mn 2 (CO)10 + 4(C 6 H 5 ) 2 CO + 4NaCl

Properties:

(i) It is a golden yellow crystalline substance having m.p. 155 oC, soluble in
organic solvents. It is slowly oxidized in air, especially in solution.

(ii) It reacts with halogens to formed carbonyl halides.

Mn2(CO)10 + X2 (X = Br, I) → 2Mn(CO)5X

(iii) It reacts with Na-metal in liq. NH3 to formed carbonylate anion.

Mn 2 (CO)10 + 2 Na ⎯⎯⎯⎯→ 2Na + [Mn - (CO) 5 ]−

liq NH3
( Mn = 0)

(iv) It react with PR3 to formed Mn(CO)4(PR3).

Mn2(CO)10 + PR3 → 2Mn(CO)4(PR3) + 2CO

Structure:

In Mn2(CO)10, two Mn2(CO)5 groups are joined by Mn-Mn bond. The

formation of this bond effectively adds one electron to each Mn atom. Mn(CO)5
does not exist as Mn has odd atomic number, but it exist as Mn2(CO)10 (i.e.
unpaired electrons of each Mn atom are used to from Mn-Mn bond). Thus,
binuclear carbonyl is formed in odd atomic number of first transition series.

As shown in the structure, five terminal CO groups are joined to each

Mn atom. This dimer is held together by Mn-Mn bond without helping from
any bridging group.
5. Dicobalt octacarbonyl, Co2(CO)8:
Preparation:

(i) By direct combination of CO with cobalt metal

200 o C, 100 atm.

2Co + 8CO ⎯⎯ ⎯ ⎯ ⎯ ⎯⎯→ Co 2 (CO) 5

(ii) By carbonylating CoI2 or CoS with CO in presence of Cu-metal or by

carbonylating CoCO3 with CO in presence of Cu-metal and H2 both act
as reducing agent.

200 o C, 200 atm.

2CoS (or 2CuI 2 ) + 8CO + 4Cu ⎯⎯ ⎯ ⎯ ⎯ ⎯⎯→ Co 2 (CO) 8 + 2Cu 2S (or 4CuI)

120 - 200 o C, 250 - 300 atm.

2CoCO 3 + 8CO + 2H 2 ⎯⎯ ⎯ ⎯ ⎯ ⎯ ⎯ ⎯ ⎯⎯→ Co 2 (CO) 8 + 2H 2 O

Properties:

(i) It is orange brown crystalline substance having m.p. 51 oC. It is soluble

in alcohol, ether and CCl4.

(ii) It is decomposed at 50 oC in an inert atmosphere to give tetra

dodecacarbonyl, Co4(CO)12.

50 o C
2Co 2 (CO) 8 ⎯⎯ ⎯
⎯→ Co 4 (CO)12 + 4CO

(iii) It is converted in to deep violet basic carbonate of cobalt on exposure in

air.

(iv) It reacts with H2 at 165 oC and 200 atm. pressure to formed cobalt carbonyl
hydride, [Co-(CO)4H+]0. [Co-(CO)4H+]0

165 o C, 200 atm.

Co2(CO)8 + 2Na ⎯⎯ ⎯ ⎯ ⎯ ⎯
⎯→ [Co-(CO)4H+]0

(v) It reacts with NO to give cobalt carbonyl nitrosyl, [Co-(CO)8(NO)+]0.

Co2(CO)8 + 2NO→ [Co-(CO)8(NO)+]0 + 2CO

Structure:

Infra-red study of the solution of this compound has shown that in

solution, this compound exists in two isomeric forms. One of these forms has
a bridge structure while the other form has a non-bridge structure. In this
structure Co-atoms are d2sp3 hybridized as shown below. Three d2sp3 hybride
orbitals on each Co-atom accept a lone paired of electrons donated by the
C- atom of three terminal carbonyl groups and form three Co←CO coordinate
bonds. Such six bonds are formed. One d2sp3 hybrid orbital on one Co atom
(singly filled) overlap with the d2sp3 hybrid orbital on the other Co atom (singly
filled) and forms one Co-Co bond. Two d2sp3 hybrid orbitals on each Co atom
(singly filled) overlap with the appropriate orbital (singly filled) on C-atom of
two bridging CO groups and form Co-Co bond. Thus, all electrons in Co2(CO)8
molecule are paired and molecule is diamagnetic.

In case of non-bridge structure, Co atoms have dsp3 hybridization as

shown below.
6. Di-iron nonacarbonyl, Fe2(CO)9:
Preparation:
(i) Fe(CO)5 dissolved in glacial acetic acid is irradiated with ultraviolet light.

UV - light
2Fe(CO)5 ⎯⎯ ⎯ ⎯ ⎯→ Fe2(CO)9 + CO
On cooling the solution, Fe2(CO)9 is ppted as golden yellow crystals.
Properties:
(i) Fe2(CO)9 forms golden yellow triclinic crystals in soluble in water but
soluble in toluene and pyridine.
(ii) It decomposes at 100 oC. It is non-volatile when heat to 50 oC it decomposes
50 0 C
as 3Fe2(CO)9 ⎯⎯⎯→ 2Fe3(CO)12 + 3CO
At 100 C it forms Fe, Fe(CO)5 and some Fe3(CO)12
o

70 o C, cool
3Fe2(CO)9 ⎯⎯ ⎯ ⎯
⎯→ 3Fe(CO)5 + Fe3(CO)12
(iii) It reacts with NO to gives Fe(CO)2(NO)2 together with Fe(CO)5 and
Fe3(CO)12.
3Fe2(CO)9 + 4NO → Fe(CO)2(NO)2 + Fe(CO)5 + Fe3(CO)12 + 6CO
(iv) Fe2(CO)9 is react with phen in acetone or benzene solution at 80 oC to form
[Fe(phen)3][Fe2(CO)8]. In pyridine, with phen it gives [Fe(phen)3][Fe2(CO13].

(v) It reacts with Na in NH3 solution give carbonylate anion.

liq. NH
Fe 2 (CO) 9 + 4 Na ⎯⎯ ⎯ ⎯ ⎯3 → Na + [Fe 2 - (CO) ] 2 - + CO
2 4
( Fe = 0)
Structure:
In the structure of Fe2(CO)9, doubly bridging CO groups are present in
addition to that of terminal CO groups.
In Fe2(CO)9, three terminal CO groups are bonded to each Fe atom. The
remaining three CO group are making a bridge between two Fe atom. i.e. there
are three doubly bridging CO groups. Since the molecule has no unpaired
electron, it is diamagnetic. There is also one Fe-Fe bond. Each Fe acquires
EAN = 18.
7. Tri-iron dodecacarbonyl, Fe3(CO)12:
Preparation:
(i) It is obtained by heating Fe2(CO)9 dissolved in toluene at 70 oC
70 o C, cool
3Fe2(CO)9 (toluene solution) ⎯⎯ ⎯ ⎯ ⎯→ 3Fe(CO)5 + Fe3(CO)12
(ii) It can be obtained by oxidation of iron carbonyl hydride, Fe(CO)4H2 by
MnO2 or H2O2
3Fe(CO)4H2 + 3MnO2 + 3H2SO4 → Fe3(CO)12 + 3MnSO4 + 6H2O
3Fe(CO)4H2 + 3H2O2 → Fe3(CO)12 + 6H2O
Properties:
(i) It is green monoclinic crystals which is soluble in organic solvents like
toluene, alcohol etc.
(ii) It reacts with pyridine and alcohol
3Fe3(CO)12 + 3py → Fe3(CO)9(py)3 + 3Fe(CO)5
2Fe3(CO)12 + 3CH3OH → Fe3(CO)9(CH3OH)3 + 3Fe(CO)5
(iii) It reacts with Na in NH3 solution give carbonylate anion.
liq. NH
Fe 3 (CO)12 + 6 Na ⎯⎯ ⎯ ⎯ ⎯3 → 3Na + [Fe 2 - (CO) ] 2 -
2 4
( Fe = 0)
(iv) It is decomposed at 140 oC to give metallic iron and CO.
140 o C
Fe3(CO)12 ⎯⎯ ⎯ ⎯→ 3Fe + 12CO
(v) It is react with NO at 85 oC to form iron dicarbonyl dinitrosyl, Fe(CO)2(NO)2
Fe3(CO)12 + 6NO → 3Fe(CO)2(NO)2 + 6CO
Structure:
A line at structure was first proposed on the basis of IR spectra, which was
supported by incomplete X-Ray study. Later X-Ray study required a cyclic
structure.
Each of two Fe atom is link with three terminal CO groups, also link with
two bridging CO group and both Fe atoms link with third Fe atom. The
remaining third Fe atom is link with four terminal CO groups and each of two
Fe atoms. Fe-CO-Fe bridges are unsymmetrical.
 METALLIC NITROSYL
Metal nitrosyls are coordination compounds in which NO molecule is
attached as NO+ ion to the metal atom or ion. In these compounds the
attachment of NO+ ion to the metal atom or ion takes place through N atom.
In these compounds NO+. In these compounds NO+ ion which is called
nitrosonium or nitrosyl cation acts as a ligand. The coordination compounds
of transition metals containing NO+ ion as ligand are metal (or metallic)
nitrosyls. Examples of metal nitrosyls are given below:
(i) Metal nitrosyl carbonyls:
Important example of this type of coordination compounds are [Co-
(NO+)(CO)3]0, [Fe2-(NO+)2(CO)2]0, [Mn3-(NO+)3(CO)]0, [Mn-(NO+)(CO)4]0, [V-
(NO+)(CO)5]0 etc.
(ii) Metal nitrosyl halides:
These compounds are represented by [Fe-(NO+)2I]2, [Fe2-(NO+)2(CO)2]0, [Fe-
(NO+)2I]0, [Fe2-(NO+)3Cl]0, [Co-(NO+)2X]0 (X=Cl, Br, I), [M-(NO+)2Cl2]0 (M=Mo or W).
(iii) Metal nitrosyl thio complexes:
These compounds are given by only Fe, Co and Ni. Examples are M+[Fe-
(NO+)2S]-, M+[Co-(NO+)2S]-, M+[Ni-(NO+)2S]- (M=Na+, K+, NH4.
(iv) Metal nitrosyl cyano complexes:
Example of this type of complexes are [Mn+(NO+)(CN)5]2-, [Fe+(NO+)(CN)5]2-,
[Mn+(NO+)(CN)5]3-, [Mo+(NO+)(CN)5]4-. Among these complexes, pentacyano
nitrosyl ferrate(II) ion, [Fe+(NO+)(CN)5]2- is the most important.
(v) Miscellaneous metal nitrosyl complexes:
Nitrosyl complexes like [Co+(NO+)(NH3)5]2+, [Co+(NO+)(NO2)5]3-, [Fe+(NO+)]2+,
[Ru2+(NO+)(NH3)4Cl]2+, [Ru2+(NO+)Cl5]2-, [Fe2-(NO+)2(PR3)3]0 etc. Among these
complexes, [Fe+(NO+)]2+ is the most important.
Preparation:
(i) Metal nitrosyl carbonyls can be obtained by the action of NO on metal
carbonyls, e.g.,

Fe(CO) 5 + 2NO ⎯95

oC
⎯⎯ ⎯→ Fe(CO) 2 ( NO) 2 + 3CO
3Fe(CO)9 + 4NO → 2Fe(CO) 2 ( NO) 2 + Fe(CO) 5 + Fe 3 (CO)12 + 6CO

Fe 3 (CO)12 + 6NO ⎯85

oC
⎯⎯ ⎯→ 3Fe(CO) 2 ( NO) 2 + 6CO

Co 2 (CO) 8 + 2NO ⎯40

oC
⎯⎯ ⎯→ 2Co(CO) 3 ( NO) + 2CO
(ii) Metal nitrosyls halides can be prepared:
(a) By the action of NO on metal halides in the presence of a suitable
metal (e.g. Co, Zn etc.) which acts as a halogen acceptor, e.g.
CoX2 + 4NO + Co → 2[Co(NO)2X]
2NiI2 + 2NO + Zn → 2[Ni(NO)I] + ZnI2
( b ) By the action of halogen on nitrosyl carbonyls, e.g.,
2[Fe(CO)2(NO)2] + I2 → [Fe(NO)2I]2 + 4CO

Properties of metal nitrosyl carbonyls:

(i) Substitution reactions: In metal carbonyl nitrosyls, NO+ ions are more
firmly attached with the metal ion than the CO groups. It is for this reason
that when metal carbonyl nitrosyls are treated with ligands like PR3, CNR,
phen etc., it is only CO groups that are replaced by these ligands, e.g.,
Fe(CO)2(NO)2+2L(L=PRa, CNR) →Fe(L)2(NO)2+2CO
Fe(CO)2(NO)2+phen →Fe(phen)(NO)2+2CO
( i i ) Action of halogens: Many metal carbonyl nitrosyls, when treated with
halogens, are converted into metal nitrosyl halides, e g . ,
2[Fe(CO)2(NO)2]+I2→ [Fe(NO)2I]2+4CO

Properties of metal nitrosyl halides:

(i) Metal nitrosyl halides react with other ligands to form mono-nuclear
complexes, e.g.,
[Fe(NO)2X]2 + 2L→ 2[Fe(NO)2XL]
(ii) Iron nitrosyl halide, [Fe(NO)2I]2 reacts with K2S and CH3CI to form dark
red compounds which have the composition, K2[Fe(NO)2S]2 and
[Fe(NO)2(SCH3)]2 and are called Roussin's salts. In these compounds, Fe is
in -1 oxidation state.
+K S +CH Cl
[Fe( NO) 2 I ⎯⎯⎯
2
→ K 2 [Fe( NO) 2 S]2 ⎯⎯⎯3⎯→[Fe( NO) 2 (SCH 3 )]2
−2KI -2KCl
 SOME METALLIC NITROSYLS

Now let us make study of sodium nitroprusside, Na2[Fe2+(CN)5(NO+)]

and nitroso ferrous sulphate, FeSO4NO or [Fe+(NO+)]SO4 which are important
metallic nitrosyls.
1) Sodium nitroprusside, Na2[Fe2+(CN)5(NO+)]:
Preparation: It is prepared
(i) By the action of NaNO3 on Na4[Fe2+(CN)6]
Na4[Fe2+(CN)6] + NaNO2 + H2O → Na2[Fe2+(CN)5(NO+)] + 2NaOH + NaCN
( i i ) by passing nitric oxide (NO) into acidified solution of Na4[Fe(CN)6].
2Na4[Fe(CN)6] + H2SO4 + 3NO → 2Na2[Fe(NO)(CN)5] + 2NaCN + Na2SO4 +
l/2 N2 + H2O
Properties:
(i) Sodium nitroprusside forms beautiful ruby red rhombic crystals which are
soluble in water.
(ii) When freshly prepared sodium nitroprusside is added to a solution
containing sulphide ion (i.e. Na2S but not H2S), a purple or violet colour is
produced. the production of this colour is due to the formation of
Na4[Fe2+(CN)5(NO+)(S2-)]. The production of this purple or violet colour is
used to confirm the presence of S2- ion in a given mixture.
Na2S + Na2[Fe2+(CN)5(NO+)] → Na4[Fe2+(CN)5(NO+)(S2-)]
(Violet or purple colour)
(iii) Alkali sulphites give a rose red colour due to the formation of
Na4[Fe(CN)5(NO)(SO3)]. This reaction can be used to distinguish sulphites
from thiosulphates which do not show this reaction.
Na2SO3 + Na2[Fe(CN)5(NO)] → Na4[Fe(CN)5(NO)(SO3)]
(iv) With silver nitrate a flesh coloured Ag2[Fe(CN)5(NO)] is produced.
2AgNO3+Na2[Fe(CN)5(NO)] → Ag2[Fe(CN)5(NO)]+2NaNO3
(v) Aldehydes and ketones containing CH3-CO-R group give deep red colour
with sodium nitroprusside and excess of NaOH.
( v i ) It is converted into sodium ferrocyanide, Na4[Fe(CN)6] on treatment with
an alkali.
6Na2[Fe(CN)5(NO)] + 14NaOH → 5Na4[Fe(CN)6] + Fe(OH)2 + 6NaNO3 + 6H2O
According to another view NO+ groups present in nitroprusside is
oxidized to NO2 and thus a nitro complex is obtained.
Na2[Fe(CN)5(NO)] + 2NaOH → Na4[Fe(CN)5(NO2)] + H2O
(vii) [Fe(CN)5(NO)]2- ion has diamagnetic character. Its diamagnetic character
confirms the fact that NO is present as NO+ ion in this complex ion.
Structure:
[Fe(CN)5(NO)]2- was formerly supposed to contain Fe(+3) ion but Pauling
in 1931 and Sidgwick in 1934 suggested that the odd electron of NO group
enters the valence-shell of Fe (+3) ion making Fe in +2 oxidation state. Thus
NO radical acquires one positive charge and gets coordinated to Fe(+2) ion as
NO+ radical. This view is supported by the fact that Na2[Fe(CN)5(NO)] is
diamagnetic where as K3[Fe(CN)6] is paramagnetic. Thus in [Fe(CN)5(NO)]2-
there are total three positive charges (Fe = +2, NO = +1] and five negative
charges due to the presence of five CN groups. Hence total charges acquired
by [Fe(CN)5(NO)] is -2. In other words, the formula of sodium nitroprusside is
Na2[Fe2+(CN)5 (NO+)]. [Fe2+(CN)5(NO+)]2- has octahedral structure with Fe2+ ion
located at the centre of the octahedron.
Uses:
It is use as a reagent in qualitative analysis for the detection of sulphides,
sulphites, aldehydes and ketones containing CH3-CO-R group.

2) Nitroso ferrous sulphate, FeSO4NO or [Fe+(NO+)]SO4:

When, to the aqueous solution of a metallic nitrate (say NaNO3) is added
freshly prepared solution of FeSO4 and a few drops of conc. H2SO4 along the
sides of the test tube, a brown ring of nitroso ferrous sulphate, [Fe+(NO+)]SO4
is obtained at the junction of the two liquids in the test tube. The formation
of nitroso ferrous sulphate takes place through the following equations:
(a) 6NaNO3 +H2SO4 → NaHSO3 + HNO3
[or NO3- + H+ → HNO3]
( b ) 6FeS04 + 2HNO3 + 3H2SO4 → 3Fe2(SO4)3 + 2NO + 4H2O
[or 3Fe2+ + NO3+ + 4H+ → 3Fe3+ + NO + 2H2O]
(C) FeSO4 + NO → FeSO4NO or [Fe+(NO+)]2+SO42-
[or Fe2+ + NO → [Fe+(NO+)]2+ ]
In aqueous solution [Fe+(NO+)]2+ ion is better expressed as
[Fe(NO)(H2O)5]2+. It is a paramagnetic substance corresponding to the
presence of three unpaired electrons, since solution magnetic measurements
give 3.90 B.M. as the value of its magnetic moment. This value supports the
fact that Fe is in +1 oxidation state in this complex ion i.e. it is a high spin
complex of Fe (+1) (3d7 system) with NO+. The complex has N—O stretching
frequency at 1745 cm-1 which indicates the presence of strong π-bonding and
the intense brown colour strongly suggests Fe+—NO+ charge transfer.
The formation of [Fe+(NO+)]2+ ion has been utilized in the detection of
NO3- ion in a given inorganic salt.
Structure and nature of M—NO bonding in nitrosyls:
According to Coulson the molecular orbital configuration of NO
molecule is (sp)2O, (σspb)2,(πyb)2=(πzb)2, (sp)2N, (πy*)1=πz*)0, (σsp*)0 [in getting this
configuration x-axis has been assumed to be the molecular axis and sp hybrid
orbital have been obtained by the combination of 2s and 2px orbital]. Now
when NO molecule coordinates with metal atom to form metallic nitrosyls, the
single electron present in πy* molecular orbital is transferred to metal atom M
so that NO molecule is converted into NO+ cation (called nitrosonium or
nitrosyl cation) and M atom becomes M- ion. Each of the atoms viz. N and O
in NO+ ion contains one lone pair of electrons in (sp)O and (sp)N hybrid orbital
respectively. Now since NO+ ion is iso-electronic with CO molecule, this ion
co-ordinates with M- ion as a two-electron donor in metal nitrosyls in the same
way as CO co-ordinates to M atom in metal carbonyls. Note that, NO molecule
is a three-electron-donor. Since O-atom is more electronegative than N-atom,
it is N-atom of NO+ ion which coordinates to M- ion metal nitrosyls. In other
wards we say that coordination of NO+ ion to M- ion metal nitrosyl takes place
through the lone pair residing in (sp)N hybrid orbital on N-atom. The
coordinate bond formed in metal nitrosyls can be shown as M-←NO+. Thus,
we see that the nature of bonding between NO+ and M- in nitrosyls is the same
as that between CO molecule and M atom in carbonyls.
On the basis of molecular orbital theory, the hybrid orbital on N-atom
containing a lone pair [i.e. (sp)2N lone pair] overlaps with a suitable vacant
hybrid orbital on M- ion (sp3 in tetrahedral or d2sp3 in octahedral case) to form
ON+→M- σ-bond. Now the empty πx* or πy* molecular orbital can overlap with
the filled d-orbitals (dxy, dyz, dzx orbitals in octahedral case and dx2-y2 and dz2
orbitals in tetrahedral case) to form M-←NO+ π-bond. This type of overlap
transfers some charge from M- ion to NO+ ion. Structural studies have shown
that the M—N bond in nitrosyls is extremely short (= 1.57 to 1.67A0) indicating
substantial double bond character.
Effective atomic number (EAN) rule as ap| metallic nitrosyls:
Metallic nitrosyls also obey the EAN shown below for certain nitrosyls.
In these cases, NO (assumed to be a unipositive ion, NO+ and hence acts as
an electron donor. Metal atoms are, therefore, in negative o state.
(i) [Co-(CO)3(NO+)]0: ēs from Co- = 27 + 1 = 28
ēs from 3 CO = 2 x 3 = 6
ēs from NO+ = 1 x 2 = 2
hence EAN of each Co atom = 36 [Kr]
(ii) [Fe2-(CO)2(NO+)2]0: ēs from Fe2- = 26 + 2 = 28
ēs from 2 CO = 2 x 2 = 4
ēs from NO+ = 2 x 2 = 4
hence EAN of each Fe atom = 36 [Kr]
(iii) [Fe (NO )2(Pr3)2]0: ēs from Fe2- = 26 + 2 = 28
2- +

ēs from NO+ = 2 x 2 = 4
ēs from 2 Pr3 = 2 x 2 = 4
hence EAN of each Fe atom = 36 [Kr]
(iv) [Mn (CO)(NO+)3]0: ēs from Mn3- = 25 + 3 = 28
3-

ēs from CO = 1 x 2 = 2
ēs from 3 NO+ = 3 x 2 = 6
hence EAN of each Fe atom = 36 [Kr]

THE END