'

""''- -,v
Octahedral
. Fig. B.4: structures of some representative homoleptic metal carbonyls
&adiDg in Metal Carbonyls: The metal-carbon bond in metal carbonyls have both <T and tr cJuuacter.
1
The metal-carbon o--bond is formed by the donation ofJone pair ofelectrons from the carbonyl carbon Joto
1 vacant orbital of the metal. The metal-carbon ·tr-bond is formed by the donation ofa pair ofelectrvns fivm

r.,,.,,rrtin~tinn t-:nmoounds 285 .

 a filled d-orbital of metal into the vacant anti-bonding pi-molecular orbital (1t*) of carbon
metal to ligand bonding creates a synergic effect which strengthens the bond between co a:~~~de. 'I\

12- ....
cJ .~ " 5
~M~C==O~

Synergic bonding
Fig. 8 .5 : Synergic bonding interactions in a carbonyl co:mplex
19_ St~hilitv nf" C'n.nrr1;--.,..-;,.. .... r,,...,..,,...,,nnTu~c• Th"" c-t-.:11h111h, nf rnmn1ex in so1ution rp_fprc, .,,. •L-
 ..,~•p•~ ~u1.upu:;J1.. l'---U\'---03l'j ll2Jir :
21. Applications of Coordination Compounds
• In metallurgical separation: Extraction of several metals from their ores involves complex fomu
For example, silver and gold are extracted from their ores as cyanide complex.
4Au + 8KCN + 2H 2 0 + 0 2 4K[Au(CN)2 ]
Potassium dicyanoaurate (I)
+ 4KOHJ 'of
I-~ ~

2K(Au(CN) 2 ] + Z n - - ~ K 2 [Zn(CN) 4 ] + 2Au ..J, ""'-{ .

Potassium tetracyanozincate (H) A ' 1.
 . cation of some metals can be achiev
fll"ff11 nickel is converted to [Ni(CO) ) ed through corn
4 1
ilflP : analytical chemistry: Cornpl 'Which is decorn::;onn~tion. For example, in Mood's process,
tJI roical analysis. ex formation is frc to Yield pure nickel.
oua• .
0 ..,,e 1•tative Analysis·
2
quenuy encountered in qualitative and quantitative
(I • Detection of Cu + is based ,
Cu2+ + 4NH3 on the fo,.,.. . of a bl
... ,at1on '1

[Cu(NJ.{ ) ]2+ uetetraarnminecopper(ll)ion. /

34
•
·2+ •
N1 1s detected by the form . Doq, blue V
/\
at1on of a rect
NiCl2 + 2DMG + 2NH OH complex With dimethyl glyoxime (DMG). ·,
'I
[N' ' p,
4

• The separation of Ag+ and H i+ .

.
l(~MG)i]
N1<ket
b,,.i;rncthylglyo,imate
X
+ 2NH4CI + 2H20
I /1

11
NH t · 1 g m group I · b , i
l
3• ormmg a so uble complex, HgiCI fo~s ase~ on the fact that while AgCI dissolves in '
AgCl(s) + 2NH 3(aq) 2 an insoluble black substance.
[Ag(NH3)i]Cl(aq) V @A~\ eV\D
Soluble cornp1.. (\. \
Hg 2Cl 2 (s) + NH 3 H . • ,'ti., d
· . g(NH2)CI. Hg + HCI V ~v-,.v-.....
, •
iJ1 Quantitative Analysis
• Black insoluble subs
lance
/'
to'(' t,.BSt
( 2
Gravimetric estimation of Ni + is earn· d 'T
1 . h e out by precip't t' N·2+ . . '
comp ex m t e presence of ammoni a. ,
I a mg I
. as red nickel dimethyl ox1me
2
Ni + + 2DMG NH3
[Ni(DMG)i]
X
Red ppt.
EDTA is used in the complexometric d • .
c 2+, Ni2+, etc.
0 , _eterminat~on of several metal ions such as ca2+, Zn2+, Fe2•,
• In Medicinal Chemistry: .
The platinum complex cis-[Pt(NH ) Cl ] · . · · . ·' · ,
cancer. , ' . · 3 2 2 , known as cisplatin is used in the treatment of

EDTA complex of calcium is used in the treatm~nt of lead poisoning. Ca-EDTA is a

weak complex· whe 1·t · d · · · ·
. , n is a mm1stered, calcmm m the complex is replaced by the lead
present m the body and i~ eliminated _with the urine.
1j ,
- ~e excess of _c~pper_ and iron pre~ent in animal sys~em are remov~d by the chelating I

ligands, D-peruc1llamme and desferrioxime B via the formation of complexes.

• In Biological System:
Haemoglobin, the red pigment of blood which acts as oxygen carrier is a complex of Fe2+
· with porphyrin.
The pigment responsible for photosynthesis, chlorophyll, is a complex of Mg2+ with
porphyrin. ·
Vitamin B12 (Cyanocobalamine), the antipernicious anaemia factor, is a complex of cobalt
• In the Estimation of Hardness of Water: The hardness of water is estimated by simple ,:,
titration with Na2EDTA. The Ca + and Mg2+ ions form stable complexes with EDTA. The
2
\
selective estimation of these ions can be done due to difference in the stability constants of
calcium and magnesium complexes.
• In Photography: In black and white photography, the developed film is fixed by washing
with hypo solution which dissolves the undecomposed AgBr to form a complex ion,
[Ag(S203)i]3-. .. .
e In Catalysis: Coordination compounds are used as catalysts for many industrial proce&ses.
For example, Wilkinson's catalyst, a rhodium complex having formula [(Ph3P) RhCl] is used
3
for the selective hydrogenation of alkenes.