30

487
aW4
TION
COMPOUNDS

IMPORTANCE AND APPLICA- Now, when the solution is saturated with H,,
TIONS OF CO-0RDINATION the ionic product does not exceed the K_ of Cu,S due to
and hence
formation of a highly stable complex ofcopper
COMPOUNDS only CdS gets precipitated.
with
co-ordinationcompounds are of great impor- Nickel ions are estimated by forming compiex
The compounds constitute the minerals, plants dimethylglyoxime(DMG). ircomplexes
These
presentin
animals These playimportant Ca* and Mg+ ions are estimated as their o
example, chlorophyll(present in plants) with EDTA.
For
constituent of blood) are both Compounds. By
tns.
ga
n(essential
haemoglobin
an 2. Dissolution of Insoluble
compounds.and are of greatimportancein are brought
complex formation, water insoluble species
rzination plants and bauxite, Al,0, 15
the various biological |functions of into solution. For example. in red sodium
le co-ordination compounds also concentrated
separated from Fe,0, by heating with
aTuatingBesidesthese.the
the formation
applicationin the fields of metallurgy, bio- hydroxide solution. Al,0, dissolves due to
s Wider rsoftening, ion exchange, electrochemis- of Al(OH, complex ion.
water
hemistry,wa
chemistry. ’ 2AI OH), (aq)
textiledyeing,bacteriologyandlanalytical precipitate Al,0,(s) +3H,00) +20H(aq)
T. EDTA and DMG are required to film is fixed by
frexample, these, the study of 3. In Photography, developed
etalslke
Nii.Zn, Cd, etc. Apart from understanding of washing it with a solution of sodium
thiosulphate.
compounds has enlarged our AgBrls) +3Na,S,0,(aq)Na,lAgS,0,),]laq)
such
certain physical properties
amplex
emjcal bonding, andproperties, etc.
+NaBrtaq)
Setral, magnetic changes the redox
co-ordination complexes both 4. The nature of ligands,
Alarge variety of in the presence
synthetically prepared are behaviour of themetal ions. For example,
saurally existing as wellas surrounded by oxidized from +2 oxidation
inOKn to us. As the central
metal ion is of someligands cobalt is easily
complexes possess dif state to +3 oxidation state.
tiferent molecular species, these Hardness of Water. The
and find many appli 5. Estimation of
irent physico-chemical properties applications of the titration against
ations in different processes. A
few hardness of water is estimated by simple
complexes with the
summarised below: EDTA solution. EDTA forms
stable
co-ordination complexes are water. Since stability
1. Qualitative Analysis.
The formation of metal ions present in the hard complexes of EDTA
reagents is very constants of calciumand magnesium
Taplex substances by using suitable estimation ofthese ions is
of cations are different, even the selective
ietively used in the separation and detection
I qualitative analysis. For example,
Group I of the possible.
co-ordination complexes
stene for qualitative analysis has Agt, Pbt and Hg,". 6. Electroplating. Many
electroplating. These complexes
u these are first precipitated as chlorides. PbCI,(s) 1s are used as electrolytes for manner. For example,
tetmOved from AgCl\s) and Hg,C1,(s) by its greater deliver the metal ions in controlled
KlAg( CN),]is used.
ability yin hot water.AgCls) isseparated from Hg,Cl,(s) for silver platingthe complex are
ty ts solubility in ) with which it forms
a soluble
7. Extraction of Metals. Silver and gold
Umplex
NH,(ag) extracted from their respective
ores by treatment with
also involves complex
AgC\s) +2NH{aq) ’lAg(NH,),] (aq) +CI(aq) sodium cyanide solution. This
could
Sim ilarly, the sepparation of Cd+ from Cut formation.
Ag'lag) +2NaCNaq) ’ NalAg(CN),Jlaq) +Na*
also be:t achieved by thesolution of Cu+2
and Cd2*
wil excessof treating Au'aq) +2NaCN(aq) ’ NalAu(CN),J aq) +Nat
of CN-.The following reaction occurs
8.Biological Uses
Ca2 +4CN Cd (CN),12 ..,= 7.1 x 10 calcium with EDTA is used to
) The complex of
u48CN 2|Cu(CN),J' +C,N,4)
. .k, = 2 x
1027
treat lead poisoning. Inside the
body calcium in
 488

the complex is replaced by lead. The more stable

Pb-EDTA complex is eliminated in urine.
Comprehensve CHEME
(ü) The platinum complex cis-(PNH,),CIJ
N
known as cisplatin is used as an antitumor agent
in treatment of cancer.
(m) Many natural compounds, exist asco-ordination N
complexes. For example, haemoglobin (a complex
of Fe2*), chlorophyll (a complex of Mg?) and
vitamin B,, (a complex of Co²* ).
VALUE BASED QUESTION 2 Porphine
Complexes derived Fe
porphyrins. the structure from
In
The co-ordination complexes are known to be having
medicinal properties. Many such complexes are being
used as drugs for the cure of contageous diseases. One
can replace the two H
atoms shown
on the abovet
co-ordinate simultaneously with central
porphine
ate
such complex is cis-platin and marketed as C DD or porphyrin is thus all four
DDP or cis-platino. satetradentate
for the central metal ion.
0) In chlorophyll the
ligandoor
cheatra
Answer the following questions: centrall
(i) What is full form of DDP and how it is prepared?
(ü) In
haemoglobin it is Fe*2 ion.ion is Mg:
The iroonn-porphyrin
(iü)As a student of chemistry explain how the cis isomer
ofDDP is used in cure of lungcancer?
group. combination is called ;
(iüü) What values are associated with the
complexes?
preparation of 9.12 METAL CARBONYLS
9. Plant Metal carbonyls of transition
Growth. Plants need various nutrients
for healthy growth. The essential nutrients include a another important elements bo
class of organometallic
d-block elements which contain only compo
number of metals such as iron, zinc, copper, called homoleptic carbonyls. carbonyl igzt:
and molybdenum. Iron in its +3 oxidation statemanganese
in the soil
is mostly hydrolysed to form insoluble iron Amond in 1890 prepared the first bom.
such as Fe(OH), which cannot be taken up hydroxides
carbonyl, Ni(C0),. Later on a large
by binary carbonyl like, Fe(C0),, CHC0),number oi
Thus due todeficiency of iron plants develop a plants. Mo C0,T
were prepared. In addition to mononuclear metal oan
disorder
known as iron chlorosis, evidenced by yelowing leaves. mentioned above, transition metals form
The standard treatment for this
problem is polynuclear metal carbonyls such as Fe
supplying Fe(III)-EDTA complex. This complex is soluble
in water and readily enters the roots of
Mn,{C0),0 The metal carbon bonds in metal ar
possess both o and character.
trees, where it is
eventually converted into a utilizable form. CLASSIFICATION OF METAL CARBONYLS
10. In Living Systems.
Coordination compounds
play many important roles in animals
Metal carbonyls are classified intotwo
are essential in storage and and plants. They () Mononuclear (or monomerie) car
transport of oxygen, as These are such compoundss whichh contain onyone
electron transfer agents, as catalysts andin atom per molecule. For example, VICO
photosynthesis. () Polynuclear carbonyls. These cnt
andareoftk
Haemoglobin, a protein present in blood serves the or more metallic atoms per molecule
purpose of carrying oxygen in the MM(CO),. These carbonyls are alsosometimes
tissues. Porphine molecule is anblood from the lungs to bridged carbonyls. Polynuclear carbonylSimaybe
important part of
haemoglobin structure and is shown below. nuclear e.g., Fe,(COi2 or heteronucleareg.

MnRe(C0o
 4ON
COMPOUNDS
489

TUREOFMETA
AL CARBONYLS
metal,carbonyls are given below:
of'some
rctures
CO
CO
...Co ....CO

OC Fe C

CO 00 CO

0C CO
CO CO

[Ni(CO)] [Fe(CO),] [Cr(CO))

CO CO CO
CO

CO CO
Fe MnOC
OC Mn
co 0C

CO CO
0C CO CO
CO
[Mn,(CO),])
[Fe, (CO),)

MENCLATURE OF METAL
CARBONYLS (CO, CoCO), CoCO),
Di-s-carbonyl bis
metal atom is in zero
ln metal carbonyls the mentioned. (tricarbonyl cobalt)
state therefore it may not be
riation two or more times Bis (tetracarbonyl cobalt)
appears
If the metal atom
added before the name
of (CO),Co Coco),
the word di, ter etc., is Tri-u- Carbonyl bis
(CO),Fe(C0),FeCO,
al atom.
bridge between the two (tricarbonyl iron)
ü) Ifthe CO groups act as
letter mu (u) is written (n°-benzene) tricarbonyl
Zas atoms then the Greek (C,H) CrCO),
HTe their names. chromium
present between
w) When metal-metal bond is (n'-butadiene)
bis, tris, etc., are
r atoms than multiple prefixes, Fe(CO), (C,H) tricarbonyl iron.
organo
D) While writing the names of n bonded
hapto (n) is used before
ut Compounds the symbol carbon CARBONYLS
of molecule indicating the number of BONDINGIN METAL in metal
ims in the carbon bonded
ligand. mentioned, the M-C bond
illustrate the As already character. The nmetal-carbon
'Ne Some
given below to carbonyls has o as well as t
oints. examples are pair of electrons
is formed by the donation of lone
G bond the metal
Tetracarbonylnickel carbonyl carbon into a vacant orbital of formed
on the r bond is
shown in Fig. 9.3. The metal-carbon filled d-orbital
Decacarbonyl as a
pair of electronsfrom
dimanganese by the donation ofa antibondingpi-molecular orbital
vacant
Octacarbonyl dicobalt of metal into the
monoxide.
Enneacarbonyldiiron (r*) of carbon
 Romprelhenae CHEST
490

O.0 C=0:

G-Overlap
M
C=0:

:C= 0: M
:C=0:

I-Overlap

Fig.9.3. Bonding in metal carbonyls.

The metal to ligand bonding creates a synergic
effect which strengthens the bond between C0and the Fe+5CO
metal (Fig. 9.4). Nickel can be
volatile Ni(CO), and purified by
firstFeCO),
subsequent
of Ni(CO), This process is convdeercotimnyg
thasermal
known Mond
C=0 PROPERTIES OF METAL pross
1. Metal CARBONYIS
carbonyls are mostly solids ar
Synergic bonding temperature and pressure. However
carbonyls are liquids.
Fig. 9.4. Example of synergic 2. The
bonding
interactions in a carbonyl complex. toxic.mononuclear carbonyls are volatilk
3.
PREPARATION OF METAL CARBONYLS
Finely divided nickel
Mononuclear
light coloured
carbonyls are either colou'e
temperature to form Ni(CO), reacts with CO at room are more deeplywhereas polynuclear
coloured. For
carter
Ni+ 4C0 is light straw coloured example.Fet
’ Ni(CO), liquid while Fe C0
Iron reacts with CO at higher adeep green solid.
pressure. temperature and 4. With exception of
Fe,(C0),,
soluble in hydrocarbon solvents. carbon's