IIIDI COORDINATION COMPOUNDS

MODERN'S abc + OF C
HE!(~
'f, ~ 'J
The coordination compounds are the co~pounds in which the l'J
metal atom is bound to a number of aruons or neutral mo} ce11trai 1
coordinate bonds. These are formed. from apparently saturated ~ea
molecules capable of independent eXIS t ence. For example wh !!table ~--
ammonia is added to green solution of nickel chloride, NiC½, the col:n aqu.eo¾
to purple. The Ni2+ ions almost disappear from_the solution. The S:
c~ang~
evaporation, yields purple crystals co.rresponding to the formula [Njtion, on
C½. Such a compound is called coordination (or c~mplex) comp0~~)~
properties of the complex compound are completely different from th 'fiie v
ions or ammonia molecules. . ose of Ni4
NiC12 + 6NH3 - - t lN1(NH 3)JC½ .1,
(Green) (Purple crystals) '
Coordination compo Vi
When the compound is dissolve~ i~ water, ~here is hardly any e.:d
Ni2+ ions or ammonia molecules. It iomses to give a new species INi(Nl{nce of l
4
Such an ion is called complex ion. 2
3)J . 1··
[Ni(NH ) JC12 - - t [Ni (NH3) 6] + + 2Cl-
36
Complex ion I

At this stage it may be noted that the species in the square br k 1i

does not ionise. It' remains as singe
· 1 ent·ti Y· It is
· kn own as complex enr ac eta I,
Differences between Coordination Compounds and Double Sal~ ty,
Though both double salts and coordination _com~~ds 8rE: formed by
coordination of two or more stable compounds m stoichiometric ratio, yet :e
coordination compounds are different from double salts. Double salts are ad.diti-0 e
or molecular compounds which are formed ?Y two apparently saturated compou~
but they lose their identity when dissolved in water. The common double salts are·
Mohr's salt FeSO4.(NH4) 2SO 4.6H2O .
Potash alum : ~SO 4.AliSOA24H2O
Carnallite : KC!. MgC12.6~O
For example, Mohr's salt dissolves in water and gives the characteristi
properties ofFe 2+, NH/ and sO 42- ions. Thus, double salts are stable in soli~
state but break up into constituents when dissolved in water.
FeSO4.(NH4 )2 SO4.6~O water Fe2+ (aq) + 2NH/ (aq) + SO42-(aq) + 61¾0
On the other hand, the coordination compounds retain their identities
in the solid state as well as when dissolved in water or any other solvent.
Their properties are completely different from the constituents (metal and
ions or molecules). For example, [Ni(NH 3) 6]C1i does not show the properties of
NiC1i or ~o~a. ~imilarly, complex ~on such as [Fe(CN)6]4- ofK4[Fe(CN)J
does not dissociate into Fe2+ and CN- 10ns.
The main points of differences between coordination compound and double
salt are summed up in Table 1.
Table 1. Differences between double salt and a coordination compound.

Double salt Coo~tion compound

1. Coordination compounds exist in the solid state as well as
1. Double salts exist only in solid state and dissociate
into ions in aqueous solution or in any other solvent.when dissolved in water or any other solvent.
2. They lose their identity in solution. 2. They do not completely lose their identity in solution.
3. The properties of coordination compound are different from
3. The properties of the double salt are essentially the
same as those of constituent compounds. the constituents.
4. In a double salt, metal ions exhibit their normal 4. In coordination compound, metal ion is surrounded by a
valency. number of oppositely charged ions or neutral molecules
more than its normal valency.
5. In a double salt, the metal ions show their normal 5. In a coordination compound, the metal ion satisfies its two
valencies. types of valencies called primary valency and secondary
valency (discussed later).
:-..~
,, coMPOUNDS·
• 110N
1 ,.,a£ORY OF COORDINATION COMPOUNDS
~
J r$tt'S,.
Jlla.IlY attempts* were 1;11ade b! different workers in the chemistry
f ~otlgh. 11 coropounds, the roam credit goes to the brilliant work of Alfred
11

~at~92. ~e prepar~d a lar~e num~er of c~ordination compounds and

/fler ill ·r physical, chetn1cal and isomenc behaVIour by simple experimental
~1ed w:\-1e isolated cobalt compounds from :he reaction of cobalt chloride and
;t~!#q~e ,rhese we.re also ~amed on the basis of the colour of the compound.
f'~oll 111 · fthe earher studies of cobalt complexes were precipitation reactions
eo t d. . '
~ 5o!ll ,ice ,neas~remen s.an isomeric behaviour, as briefly discussed below :
Jutta cipitation ~tudies. Th~ ~umber of ions furnished by a complex in a
I' 1: ri:iill be dete~ned by ~recipita_tion reactions. For example, the number
~11°~ ill a solution ~f vanous ammes were determined by the treatment
1 115
~er \ver 11itrate solution. From the amount of white precipitate of AgCI
;t!J per roole of the compound, the number of CJ- ions can be calculated.
fof1lle aJllple, when the ~ompound CoCl.3,6NH3is treated with excess of AgNO ,
fore[ of Agel_ 3:e obtamed from 1 mol of the compound i.e., all the three d-
s!ll0life pre~1p1tated. On the other hand, when the compound CoCl3.5NH3
jo~~ated with e~c~ss of Ag~03, 2 mol of AgCl are obtained i.e., only two
ii jS jons are precipi~ate?· This means_ that the compound CoCl .6NH , has
!
· Cl jo!lizable chlo:1d~ ions where~s lil the compound CoCl3.5Nil3, onfy two
t!#e. e atoros are 10ruzable as Cl- ions.
c!Jl01111 AgN03
coC1 .6Nlis 3AgCl (corresponding to 3 Cl- ions)
3 AgN03
coC1 .5Nli3 2AgCl (corresponding to 2 c1- ions)
3
Similarly, the number of chloride ions precipitated in the case of the
c0P1P 0unds C0Cl3.4NH3 and CoCl3.3NH3 have been found to be 1 and none.
2, Conductance measurements. The measurement of molar conductances
(,\,i) of solu~ions of coordination compounds helps to estimate the number
f s furrnshed by the compound in solution. By comparing the molar
1011
~nductance of t~e compound with those of some known electrolytes, Werner
was able to predict the number of ions present in the solution. For example,
•tbas been observed that the complex CoCl3.6NH3behaved as 1:3 electrolyte,
coC1 .5NHa. as 1:2 electrolyte, CoCl3.4NH3as 1:1 electrolyte. The coordination
compound
3 coCl:i:_3NH3 behaved as a molecule (non-electrolyte). These results
are recorded in Table 2. .
Table 2. Series of coloured coordination compounds isolated by the reaction of C0Cl 3 and NBs·
Moles of No. of Behaviour as
Colour Name according
Compound
to colour AgCl formed c1- ions electrolyte I
I

3 3 1:3
CoCl3.6NH3 Yellow Luteo complex
CoCl3.5NH3
CoC1a.4NH3
Purple
Green
Purpureo complex
Praseo complex
2
1
2
1
1:2
1:1
1: 1
!'
I
Violeo complex 1 1
CoCl3.4NH3 Violet
0 0 Non-electrolyte
Red Roseo complex
CoCl3.5Nlis-~O
3. Isomers of compounds. Werner attempted to assign structures of
different coordination compounds by comparison of the number of known • Primary valency corresponds to
isomers and the number of theoretically possible structures. oxidation number
AP, a result of extensive experiniental studies, Werner proposed a theory
known as Werner's coordination theory. In recognisation of his work in this • Primary valencies are satisfied
by negative ions.
field, Werner was awarded Nobel prize in chemistry.
Postulates of Werner's Coordination Theory
• Secondary valency corresponds to
1. In coordination compounds, metal atoms exhibit two types of valencies coordination number
namely, the primary valency and the secondary valency. • Secondary valencies are satisfied
by negative ions or neutral
• The discovery of hexaamminecobalt(III) chloride, CoC13.6NH3 by Tassaert is
molecules.
generally regarded as the beginning of coordination chemistry.
 MODERN'S abc + OF CHE"M1s
lll-Y, :
The primary valency is ionizable ~hereas the secondary valency i
ionizable. In modem terminology, the prunaryvalency corresponds t o ~ ~-
state and the secondary valency corresponds to coordination nllll'lbe,- tic
2.. Ev~ry metal atom has a fixed number of secondary valencie~.' i.e.,
coordination number. ·
3. The metal atom tends to sati~fy both its pri,:na-7 as well as seco
valencies. Primary valencies are sati~fie_d by negative ions whereas secoIlda,
valencies are satisfied either by negative ions or by neutral molecules, In Ilda.
cases, a negative ion may satisfy both types of valencies. certa;
4. The secondary valencies are always directed towards the fixed p ..
in space and this leads to defin~te geometry of the ~oo_rdinat~on compo~5:!a1-01
other words secondary valencies have charactenstic spatial arrange · 1
corresponding ' to different
· · · numb?rs ..Ith
coordination n e modern teflllinoJ Ill.en
such spatial arrangements are c~ed coo~dinat1on polyhe~a (discu~
later). For example, if a metal ion has six secondary valencies, these BE
arranged octahedrally around the central m~tal. ion. If the metal ion Ill
four secondary valencies these are arranged m either tetrahedral or 8 hi
planar arrangement aroi'.md the central metal ion. The secondary vaieii~
thus, determine the stereochemistry of the complex. On the other hand
primary valency is non-directional. ' '
ti
Thus, a metal atom exhibits primary valen~i~s i~ the formation of its s
(e.g., CoC13 , AgN03 ) while the metal atom exhibits its secondary valencie al!
the formation of its complex ions (e.g. , [Co(NH3 )6] 3+, [Ag(NH3) 2]+; etc.) 8 1
Structures of Coordination Compounds on the Basis of Werner's Theo
The Werner's postulates helped to explai~ the structu~es of various cob:
ammines. For example, let us try to explam the bonding m coordinati
compounds of cobalt on the basis of postulates of Werner's theory. 0

/ I. CoCl3 .6NH3 • Cobalt has primary valency (oxidation state) three an

secondary valency (coordination number) six. As a convention, secondll!
valencies are represented by thick lines(-) and prim~ valencies are show
by dotted lines(.... ). In the complex, all the 6 secondary valencies are occupie
by six NH3 molecules. The CJ- ions are bonded to Co by three primary valencie
These chloride ions are ionisable and, therefore, can be precipitated on th
addition of silver nitrate. The central metal ion and the neutral molecules or ion
aigands) satisfying secondary valencies are written in a square bracket whii
writing the formula ofthe complex compound. Thus, the coordination compoun
may be formulated as [Co(NH3 ) 6]Cl~ and may be represented as shown i
Fig. 1. The primary valencies are ioruzable and therefore, all the chloride ioE
would get precipitated on the addition of silver nitrate.
Fig. 1. Representation ofCoCl,,.6Nffa
The species within the square brackets are also called coordinatio
complu: according to Werner
entities (or complexes). The ions outside the square brackets are calle
theoey. '
counter ions.1"1:1us, !11 the c?ordination c?mpound [Co(NH3 )~Cl3~ [Co(NH )Jl
3
represents coordination entity and 3CI- ions represent counter ions.
The ionisation of the coordination compound is written as :
[CoCNlia)JCI3 [Co(NH3)J 3+ + 3CI-
can be precipitated
2. CoCl3.5Nlla. In this compound, the coordination number of cobalt is
but now five positions are occupied by NH3 molecules and the sixth positio
by one of the chloride ions. This chloride ion has dual character as it satisfiE
secondary as well as a primary valency as indicated by a full line as well e
a dotted line, as shown in Fig. 2. The two CI- ions satisfy the nmiainin!~
primary valencies of cobalt. This satisfies 6 secondary and 3 primary val
ofcobalt. However, on ionisation, only two Ct' ions will be precipitated
one CI- ion which also satisfied seco.n,,dary ~ ' will not be, pr,ecipita
Thus, the coordination compaund ma) be:tormdlated 81
1 1
, ~rJi'11orJ
/
cor.4p0lJNOS
the compou_nd CoC13.4NH3, two chlorid~ ions e?U1!bit dual
~ s·. 111 ·ng both pnmary and secondary valencies. Th~s 1s shown
coClf f se.~t;ve precipitate with silver nitrate corresponding to only
•..ctet 0Jt withe number of ions in this case is 2. It may be formulated as
H3N""' I/
Cl

NH3
-
eo - - c
~et~(~
Jd1::d r·!l e.nd
i- 10

p coC½3)t~II3)4]Cl '<"""
· · as ·.
Cl and 1on1ses
[CoC½(NH3)4]+ + c1- ..
can be prec1p1tated H3N/I~
Cl NH3
1· · Jn the compound CoCl .3NH three chloride ions satisfy
c1s,srUJ:;condafY valencies as shJwn J'
Fig. 4. It is clear fr_o1!1 the [CoCl 2(NHa)JCI
kc~ e.11~ the chloride ions are non-ionisable and will not be prec1p1tated
f~tM·di\on 1 of AgN0 . Therefore, the coordination compound behaves as Fig, S. Representation of -~:4NH,
3
fil'iJie ad ~onducting molecule. It may be formulated as [CoCiaCNH3)3l and complex according to Werner's
theory,
bf al poll·.
,~tr t jon1se. ___,.
/IJll' 110 [CoCJ}NII3lal . .does not ionise
utral coordination entity and no counter ions.
!le
Jt Ji8S r also explained successfully
· the structures of amine complexes of
we~:ese are su~ed up in Table 3.
yt(!\'l· fable s. Behaviour of coordination compounds of platinum,
rJllula Present Mode of Total no, of ions
fo representation ionisation (in solution)
NH3
[Pt(NH3)6]Cl4 [Pt(NH3)J'-' + 4CJ- 5
ptCI .5NHa [PtCl(Nlia)JC~ [PtCl(NH3)i• + 3CJ- 4 [CoCl3(NHa)~
2
CoCl,,.3NHa
4
ptCI,.4NHa [PtCll Nlia\lCl:i [PtC1:i(NH3)4J • + 2c1- 3 Fig, 4. Representation of
rtCVNHa [PtCla<Nlial3]Cl [PtCJ3CNHa)3J• + c1- 2 complex according to Vfemets
ptCI .2NH3 [PtCli NlialJ 0 theory,
4
3

I
[J EltllJllpleL.- - - - - - - - - - - - - - - - - -
How many ions per mole of the following complexes are present in their
solution?
(i) [CoCl(NHJtJCl 2 (ii) [Ag(NHJ 2)Cl
(iii) [Pt(NHJ ][PtCl41 (iv) fJ'tCl 3(NHJ 3 ]Cl
4
Solution : The number of ions per mole of the complexes in the solution can be
predict.ad from thell' modes ofionisation. It should be noted that the species in the coor-
dination sphere do not ionise, , . . •
2
(i) [CoCl<NHa)JCI, a [CoCICNHa)J • + 2c1-
•, . . Smolofions
(ii) [Ag(Nlia)iJCl = ~ )2]• + CJ-
• · , 2 mol of ions
(iii) Wt<Nlia)J~ • !NNHs),]2+ + [PtC14JZ-
2 mol of ions
' and anionic parts are compleus.
01 • (PtClaCNHa)aJ+ + CI-
2 mol of ioua ·
D
- Solution :
(i)
(ii)
(iii)
[Pd(NH
2
H [PtC161
) JC1
34
[Ni(H 0) ]Cl
6
2
2
MODERN'$ abc + OF CH

Secondary valence= 4
Secondary valence= 6
Secondary valence = 6
E1,t1Sl'Ji
1

'r,~

2
(iv) [CoC1 .(NH )4)Cl Secondary valence = 6
2 3
(v) [PtCli NH )2] Secondary valence = 4
3

SOME IMPORTANT TERMS USED IN COORDINATION C ~

Some important terms used for the description ofcoordination compo lJNns
Coordination Entity or Complex Ion and Coordination Sphe: dsare;
A coordination entity constitutes a central metal atom or ion bo
to a fixed number of oppositely charged ions or neutral moleculell<ied
. !or example, (CoCliNH3)3) is a ~oordination entity, in which the CObaI a.
10n 1s surrounded by three ammoru~ molecul~s and three negatively ch t(+3)
c~oride ions. Other examples are [N1(CO\l, [N1(NH3)5) 2+, [Fe(CN\J~, lPtc?~
IN1Cli~O)4), etc. 4] ,
The central metal atom or ion and the molecules or ions bo
to it are enclosed in a square bracket and is collectively calle~
coordination sphere. the
This part of the complex behaves as one unit and is non-ionizable It .
generally written in square brackets, [ ]. The ionizable groups (or ion~) 18
written outside the brackets and are called counter ions. For exam
in the coordination compound [Co(NH3 \Cl2)Cl, the coordination entiti ~•
18
r
[Co(NH3)4C1:iJ+ and Cl- ion is counter ion.
The coordination entity (or complex ion) may be positively charged
negatively charged or a neutral species. or
r -C~ti~m:; c~mpl;;_ A co,,;pl,; ion -~r c~~di~~n e~tity ~hi.ch ha, .
inet positive charge is called cationic complex. For example, a
! [Co00Js)J 3+, [Ni(NH3)J 2+, [CoC~(NH3).)+ ,j
! Anionic complex. A complex ion or coordination entity whi.ch has a net1
jnegative charge is called anionic complex. For example,
! [Ag(CN)2J-, [Fe(C2O4)3]3-, [Fe(CN)J4- .
Neutral complex. A complex or coordination'entity which has no
, charge is called a neutral complex or simply a oomplu:. For example,

~----·-···-·----"'-·~~~~~!~~«!>L~>,~ *_,_,"~· -
Central Atom or Ion and Ligands
The atom or ion to u,hich a fized number of neutral molecule, or
ion, are attaehed in the coordination entity is called central atom
or central ion. , . ., .
The neutral molecule, or ion, bonded to the central atom or ion
in the coordination entity are called ligand&
Thus, in the complex ion lNi<NHa)sJBt, -the Ni2+ ion is the central •
and the molec:ules of ernrnonia are the · • • irin t1i'e •
leoa.ma> 1cua., the ion a
and chJorida iona1Ul8
'I'
coPIIPOUNDS
,,i''~,A'flON tral Illetal atoms/ions are also referred to as Le .
ese centtached to the central metal atom or ion th WIS aCids; The
11
.

lll"e. a essential, therefore, that while the central roug!.i c~rdinate

t,JS• It orbitals, the ligands should have lone pairs of ~e ct ion. shoul_d
-
·,l v11cll11 bitals which can be donated to the central .0 rons m their
The number of coordinating or
i''~ost or the combination of a Lewis acid (the cent:af' t~ may als~ be
ot'~,#5ed nbser of Lewis bases (ligands). The atom in the li~ge datohi~ ohr ion) ligating groups present .in:
a
''" !lJll • · all d d an w c can ligand is called the denticity
•~-~ 9 11 be electron prur is c e
,iv• te t · ( . NH ) onor , atom or coordinat'mg atom of the ligand.
JOJl9 _.,,ple, ill ammoru~, +- d. 3 ' rutrogen is the donor atom and
Pt eJ'IV"' • ou ) oxygen 1s the onor atom.
fO (~. i'2 .
let, ligand 1s
fbll~lecule or ion w~ich is capo.bk of tk,nating a pair ofekctrons to
tJrl central ,netal or wn and fonns a coordinate bond with it. ·
tJrl f Ligands
.'f~;e
f1Pes 0ligands Illay contain one or more than one donor atoms for coordin t ·
central atom. Accordingly, th~ ligands ~re classified as followt ion
11'1~.) 1Jnidentate or monodentate ligands. Ligands which can coordinate
h;central io~ through only one donor ato7!1, are known as unidentate or
IO t dentate ligands. The examples of urudentate ligands are:
lll0110 NH3, H20, c1-, cN-, oH-, 02-, N02-, co, etc.
SoJlle conunon unidentate ligands and their donor atoms are listed in Table 4.
Table 4. Some common unidentate ligands. ' Donor atom
Donor atom Name of ligand Formula
Formula OH· 0
NaJlle of ligand Hydroxide ion
i;;---- H 2O 0 NorC
CN·
water N Cyanide ion N
J\Dlll1onill NH3 NO2-
N Nitro 0
pyridine (py) C 5Hi;N ONO--
co 0 Nitrito 0
carbonyl N Oxide ion
NO SCN- SorN
Nitrosyl p Thiocyanate
(C;£5)3P c11acoo-- 0
Triphenyl phosphine Acetate
X'"{X.=F, Cl, Br, I) X
Halide ion
(ii) Didentate or bidentate ligands. Ligands which have two donor atoms
NOTE •
and therefore, can coordinate to the central ion at two positions, are called
didentate or bidentate ligands. The examples of didentate ligands are : . ; benot.edthat
CH,NH, ' 11t6=
0=9-ot I
ofel
[o=t-oJ CH,NH,
Ethylenedirunine (en)
Oxalate ion
Ethane-I, 2-dirunine
Oxal~te ion is abbreviated as ox and ethane-1,2-diamine (ethylenediamine)
is abbreviated as en.
Glycinate ion, C~~)COO- (abbreviated as gly) contains two different
donor atoms N and 0. / NH ·
c~ 2~

~coo-/
Glycinate ion
Similarly, 2, 2-dipyridyl (abbreviated as clipy), orthophenanthroline or
1, 10-phenantbroline (abbreviated as phen) act aa didentate ligands.

ON
 MODERN'S abc + OF CHe,.c,
NH2 NH2 . d . hi h h
On the other hand, the didentate 11gan s !11 w
Slltr,i
t e two coordin .

H2C
/ '\ I \ CH2
groups are different are called unsymmetncal didentate ligand atlll
example, glycinate ion (NH2CH2COO-). . 8
• F'a
(iii) Polydentate ligands. Ligands having more than two dono
I I present in the molecule are called polydentate ligands. These may ato1ri,
H2C\ / \ /CH2 tri or terdentate (three), tetradentate (four), pentadentate (fi. Calle,
hexadentate (six) ligands depending upon the number of donor atom Ve) an1
NH'-. NH in their molecules. For example, s Presen
c-c.,.....
H2 H2 • Diethylene triamine (abbreviated as dien) acts as tri or terdentate Ii
having three donor N atoms (page 7). gillie
Triethylenetetraamine (trien) • Triethylene tetraamine (abbreviated as trien) acts as tetradentate Ii
or N, N'-bis (2-aminoethyl) ethane-I, having four donor N atoms and glllicl
2-diamine (tetradentate)
• Ethylenediamine triacetate ion acts as pentadentate ligand havm
g two
lo--c==o
N atoms and three O donor atoms. .
?i/o- • Ethylenediaminetetraacetate ion (abbreviat~d as EDTA), is an impo

\~~v
le "'-. o-'c::o~ hexadentate ligand. It binds through two mtrogen and four oxygen ~t
H2C I 'c CH2 to a central metal ion.
8
Ills

-oocH2C t t/ CH2COO- '-..

HN\ /N / ""N-CH2-CH2-N

"'-ooc
2 H/ ~CHCOO-/ 2
CH2 - C H2 (EDTA)4-
Ethylenediamine triacetate The various polydentate ligands which generally take part in the fonnati
(pentadentate) of complexes are given in Table 5. on
Table 5. Some common bidentate and polydentate ligands.

_ Name__,;;.__
of lifBDd _ _ _;_;_:_:,:...:.:.=..:=-----==:.::..:.:.:.:=----:-.;,.;,,:,.:_;,:;_;.;:.:::_....,.._
Structur&'Formula Donor atom Abbreviation _ _ _,
Bidentate ligands

C1¼ -C~

Ethylene diamine
I '\ N

c~
Onlate ion
I
coo-/
0

,1
Glycinate ion NandO
~coo/
' . lfaC-C--CH = y-CHa 0
Acetyl acetonate

Dimethyl glyozimato
CH,-C=N-~
. I
CH,-C=N_..,..
I
OB
r uN_o_s__:'.""'_:-:-.::::=-:::---------=---=--------;;:;::::~~;--
,011 c;"o:,_.:p:o~
structure/Formula Donor atom ~dOII
•
Tcrd1mt11t<' lig11nd>1

N did
,. tria.tll1ne
.
telle
~etJli

I
N I trim

·etJlytelle.
fr1
tetraaroine
!'
I;'
Pl'nladcntate ligands I
>
lt .
r
NandO
diaroine triacetato
ttJil'1e11e

Hexa dentate ligands

Ethylenedi~e NandO
ietraacetate ,on

Chelation and Denticity

When a didentate or a pol;ydentate ligand UIU!B it• IUJo or more
donor atomB to bind to the •ame central metal atom or ion forming
a ring •tructure it is called chelation.
The resulting complex has ring structure and the ligand coordinating through
two or more donor groups is called chelating Jiarand. Some common eumplea
of chelating ligands are : carbonate ion, oxalate ion (or-), ethylenediamine
(en), ortho-phenanthroline (phen), ethyleJ1ediarnine t.a
etc. Their structures are given in Table 6.
The word chelate is derived from Greek word
mmplex is called chelate. For uami>,le, wliin
ethylenediamine attachee t.o Cu..,
I ring structure, it is called
l~CU.'-'~IJ::Walia
 H2
Cl'- ,.,,. ,-N-.CH
I 2

Cl/ "N/CH2 Chelating ligand

H2 The number of coordinating ?r ligating groups present in a Ii
IPtCl/en)J is called the denticity of the bgand. Some common examples are~¾d.
Structure (a) 1. Didentate chelation ·
In this case the chelating ligand coordinates through two sigma el
pair donor grou~s. For example, [PtCl/en)J where en represents the did ectron
CH2-CH2 ligand NH CH CH NH (ethane-1 2-diamineorethylenediamine) (Struct entat@
2 2 2 2 ' llre(a)J
2. Terdentate chelation ·
~Pt/)HrH, In this case, the chelating ligand coord~na~s thro~gh three electron .
donor groups. For example, in the coordmation entity IPtCl(dien))+ :.air
[N-(2-aminoethyl) ethane-1 2-diamineJ is a terdentate ligand [Structiu'. 1en
Cl/' ~N/CH2 8. Tetradentate cheI~tion e (b)].
H2 In this case, the chelatin~ ligand _coor~nat~s throug~ f?ur electron .
donor groups. For example, m IPt(tnen)J , tn~n IN, N -bis-(2-aminoethair
IPtCl(dien)J+ ethane-1, 2-diamineJ represents a tetradentate ligand [Structure (c)]. Yl)
Structure (b)
It may be noted that
• Chelate ligands form more stable complexes than similar ordin
complexes in which the ligand acts as monodentate. This is called che}a~
effect.
• The chelate complexes containing 5 and 6 membered ring
1
are comparatively more stable.
• In general, chelating ligands which do not contain unsaturated grou
i.e. double bonds (e.g. ethylenediamine) form five membered stable rin~
On the other hand, chelating ligands containing unsaturated groups (e.g.
acetylacetone) form six membered stable rings. ·
• Due to steric hindrance, ligands with large groups form unstable
compounds as compared to the analogous ligands containing smaller groups.

Ambident ligands
The morwdentate ligands which can coordinate with the central atom
through more than one site are called ambidentate ligands.
· These ligands contain more than one coordinating atoms in their molecules
For example, N02 can coordinate to the metal atom through N or o as ·
0
.M . - N / M+--0-N=O
~o
nitro or nitrito-N nitrito or nitrito-0
Similarly, -CN can coordinate through C or N as
M +--CN . M+--NC
cyanide isocyanide
Thiocyanato (SCN) can coordinate through S or N ..
M + - - SCN M ..:-:- NCS
thiocyanato isothiocyanato
Coordination Number
· As will be shown, the ligands in a coordination compound are att.ached to
the central metal ion through coordination bonds. · · ·· -
The total number of ligands attached to a central metal atom or ion
is called the coordination number of that metal atom or ion.
In other words, coordination number is the number of l~ t m
coordination sphere of the complex. comp<Jurul.
For eum.ple, the coordination l1Umber o f ~ •
plexes are : .
r ,.,coMPOUNDS
~i\,,o
pi,I i- C.N. of Ag+ = 2
/ t,t.Cr-Oz 1z+ C.N. ofNi2• = 4
Oxalate ion ( C 204 -) • nd
2
~i (~)4 C.N. of Pt4+ 6
ethylenediamine (en) are bidentate
[ftc!t;l ) 1z+ C.N. ofCu2• = 4
ligandA and therefore, one bident.ate
[Cll(!'11!N1! ) ] C.N. of Co 3+ = 6
ligand1houldbec:ountedaatwoligllnd&
[CoCl3~ ) f:i-3 C.N. ofFe3+ = 6 Therefore, three bidentate Uganda
[fe(Cz) j3! C.N. of Co3• = 6 make C.N. "'6.
co(eJl 3 • •
I !lated that the molecules or ions present outside the square bracket It i1 important to note that
Jt Jlle.Y.: sphere) are not counted in the coordinatio~ number because these coordination number of the central
p :Jlded through coordinate bonds to the metal ion. For example, metal atom or ion ia determined only
I oot~j(!~•·3
.TU' ) JC!i
6
C.N. of Ni2+ = 6 by th.e number of l!igma bonds formed
by the ligand with the centnl atom or
cHrUJ3)JC12 C.N. of Co3+ = 6 ion. Pi bonda, if formed between
[CO
ge of a ?omplex ion . the Uganda and the central atom
Cblll"rge camed by a complex ion is the algebraic s~m of cha~ges or ion are not counted for this
~1ia bY the central metal ion and the ligands coo~~n_ated to_it. p~.
,ffled le [Ni(NH 3Js] 2+ carries a charge of +2 because Ni ion carnes a
CV" "l}lllP '
for ee of +2 an d ammorua.
molecule is neutral.
ell~ 1·(rUJ3)l+ : Charge = +2 + 6(0) = +2.
~ 'JarlY, the comple~ io~ [Co(NHa\C1]2+, carries a net charge of +2 because
. S~ed by the coor~mation of one c0 a+ ion with five neutral molecules of
itls fo .a and one Cl- ion.
,,,noOI
i r c0Cl(Nlial~l + : Charge = +3 - 1 + 5 (0) = +2
2
.
1
p. coordination compound sometimes may not have any charge. For example,
coJJJ.plex [CoCls<~a)al carries no charge because Co3+ion carries a charge
j)le 3 t,hree ammorua molecules are neutral and three Cl- ions carry together
of;~ge of -3.
a [CoCia<NH3)3l : Charge =3 - 3 + 3 (0) =o.
()sidat!on ~umber or oxidation state of the central me~ atom
The oxidatwn number of the central atom is the charge it would
rr'I if all th~ ligands are removed alongwith the electron pairs that
~re shared with th3~. ~entral a_tom_. For example, the oxidation number of
cobalt in [Co(NH3\l ·. is +3. Oxidation number is represented by a Roman
uJlleral in parenthesis.
° Calculation of oxidation number of central metal atom in a complex.
!(nowing the charge of the complex ion, we can calculate the oxidation number
fthe central metal atom. For this, the oxidation number of the central metal
;tom is assumed to be x and ~he _oxidation nu~ber of all other species are
substituted. The sum of the oxidation numbers is equated to the total charge
of the complex and the value of x is calculated. This may be illustrated by
the following examples :
[Ni(NH3)6] 2+ x + 6(0) = + 2 or x =+2
O.N. of Ni = + 2
[CoCl(NH3)sJ2+ x - 1 + 5(0) = + 2 or x = +3
O.N. of Co = + 3
x + 3(-2) = - 3 or x = +3
O.N. of Fe = +3
4(+1) + X + 6(-1) =0 or X =+2
O.N. of Fe = +2
X + 4(0) =0 or x=O
O.N. of Ni = 0
[Cu(CN\]3- x + 4(-1) = - 3 or x = +1
O.N. of Cu = + 1
These calculations will be used while writing the names of these compounds.

r
 MO DEAN'S abc + OF CHEMISlJi"

Coordination Polyhedron .
. ,,~
The· coordination number ~f a central metal ion i~ the coord· .
compound determines the spatial arrangement of the ligands aro IIlatroii
central atom or ion. ,· ll.nd the
Coordination polyhedron is the 1patial arrangement of the •
atom, which are directly attached to the central atom. 118all(t
For example, (Co(NH3)6]3+ has octahedral geometry, 1PtC! J2- has
4
planar geometry and (Ni(CO)4) has tetrahedral geometry. The shapes of co8quare
coordination entities such as tetrahedral, square planar, octahedral lllnioti
pyramidal, trigonal bipyramidal, etc., are given in Fig.5. ' square

~ L L~L ~L

L L L L L L
L·
Tetrahedral Square planar Octahedral Square pyramidal Trigonal bipyj,lilllida!

FJs. S. Shape, of tetrahedral, square planar, octahedral, square pyramidal and trigonal bipyramidal coordination polyhedr -
M represent, the central atom or ion and L represents a unidentate ligand. a.

Homoleptic and Heteroleptic Complexes

Complexes in which the metal is bound to only one kind of donor grou
(ligands) are called homoleptic complexes. For example, INi(Nl! )Jf.8
[Co(NH3)sJ 3+, [Fe(CN)6]4- are homoleptic complexes. 3 '
The complexes in which the metal is bound to more than one kind of don
groups (ligands) are called heteroleptic complexes. Some common exampl:r
of heteroleptic complexes are [NiC1:i(H2O)4), [CoCliNH ) )+, etc. 8
34
The different terms in [CoCI:i(NH3) 4)Cl are illustrated below:
Coordination entity or coordination sphere
I

(NH ) ·]+er
[CoCl~ -~ -
.I
3 --:Ionizable part
:-:-1 (Counterion)
Central Ligands C. N. =2 + 4 =6
metal ion
These are also illustrated by the following examples as given in Table 6.
Table 6. Examples of common terms used in describing coordination entities.
Cciordmation Ligand -_ Central metal Coordination
number
 9/13

r,4pout-1OS
~co
~'(lo SOLVED
l
~I'' le 3the
-- · t ion
- d ma
coor · entities and counter ions in the fo llowing
.
ff . 71ate. compounds
1;1;r1a;id
~;c
1 1)15

1
l
oJH} 5JCl2
(ii) KiNi(CN) 4]
(iv) KiFe(CN) 6]
1r.11!
• ) . (i) 41The coordin a t·ion entities
[J•, rj(CO) .. and counter ions are :
/~ ·oP •
:,allltl Coordination Counter
entity ion
[PtC1 ]2- K•
4
iric1 41 [Ni(CN)ii- K•
[il j(.l(l'li(Crl)4l [CrCl(NH3\J2• c1-
ii )(.1rCl(J-IJ:l3ls]Cl2 [Fe(CN)J4- K•
i [fe(CJ-ll5l [Ni(CO)4] § A ~ a , ~ p,.oblemS §
,i1 ~-(co\l - =
4 (iii) 6
(i) 6 (ii)
1, (vi) 5
(iv) ' 6 (v) 8
(vii) 3 (viii) 6
i111 W)lat is the coordination number of the central metal ions in the following +2 (ii i) 0
2. (i) +3 (ii)
. ordination compounds ? :+-3
1 ~il [PtCl/enl2l (ii) K 4 [Ni(CN)4J (iii) [Fe(edta)J- (iv) (c) +3
(a) +3 (b) +3
(ivl [Fe(enl ]Cl3 (v) [Mo(CN)J4- (vi) Fe(C0) 5 8,
3 +2 (e) +3
~-
(d)
(vii) (Rh{P(C 6H_5dll 3tl_Cl ~viii) K:J!Fe<C 20 4) 3J (ii) +3 (iii) 0
(i) +3
\\lbat is the oxi a 10n state of iron in the following?
(iii) Fe(CO)5 (iv) -1
(i) [Fe(CN)J3- (ii) K4 [Fe(CN)J (i) Pd4+; H,O, ONO-, r; 6; +4
I,
(iv) [Fe(HP\J3• (Co(en) ] 3+ becaUll8 it i.8 a chelate,
S. specify the oxidation numbers of the metals in the following coordination entities: 8. 3
complex.
(a) {Co(CN)(en)/~O)J 2+ (bl [CrClaCNH3)3J (cl (CoBr2(en):J•
I-
(d) [PtC1 4l2- (el Ka!Fe<CN)J
(Jharkhand Board 2013, Assam Board 2019)
,. calculate the oxidation state of the central metal atom in the following :
(i ) [Fe(EDTA)J- (ii) [Co(NO2VC 5H 5NVNH3)2]N03
(iiil K [Ni(CN) 4l (iv) Na[Co(COJ.l
. indicate4 the central metal ion, ligands, coordination number and oxidation state
5 of the central metal in the following complex :
[Pd 1 (ONO)/~O) ] 3
s. Which of2the following 2is expected to be more stable : [Co(en)3] + or
{Co(NH 3\J 3+? ·

{UPAC FORMULATION AND NOMENCLATURE OF COORDINATION

COMPOUNDS
Coordination compounds are formulated and named according to the system
set up by Inorganic Nomenclature Committee of the International Union of Pure
and Applied Chemistry (!UPAC). It is called IUPAC System of Nomenclature.
According t.o the latest (2004) IUPAC system, the following rules are observed
for writing formulas and naming mononuclear coordination compounds.
Rules for Writing Formula
The formula of a compound is a shorthand method used t.o provide basic
information about the constitution of a compound in a concise and convenient
manner. The following rules are applied while writing the formulas ;
(i) The formula of the cation whether simple or complex is written first
followed by that of the anion. . . .
(ii) The coordination entity 1s wntten m square brackets.
(iii) The sequence of symbols within the coordination entity is : first the
symbol of the central metal atom followed _by ligands in alphabetical
order. According to latest IUPAC reco=endations, the placement of a ligand
in the list does not depen d on its charge. "\. ..
'Ii f.
Ill
The ligands in coordination entity are
arranged as :
(a) The different ligands are arranged
alphabetically according to
the first symbol of their
formulae. For example, H20,
NH3, NQ 3- , SO/- and OH-, etc.,
are cited at H, N, N, S and 0 .
The ligands containing carbon and
hydrogen are cited only under C.
(b) When the two ligands have same
defining atom, the ligand u,ith
feu,er •uch atom.11 is cited fjnt
followed by the ligand having
more atom&
For example, NH3 precedes N2
(c) If the numbers of defining
atoms are equal, subsequent
symbol decides the sequence.
For example NBi- precedes N02-
because H comes before 0 .
(d) Polydentate ligands are also
listed alphabetically. In case
of abbreviated ligand, the first
letter of the abbreviation is used
to determine the position of the
ligand in alphabetical order.
• In the old system, the halide
ligands were named as :
F- : tluoro Br : bromo
CI- : chloro 1- : iodo ·
However, according to 2004
IUPAC recommendations
anionic ligands will end with
'o'. In general, ifthe anion name
ends in 'ide, 'ite' or 'ate' the
final 'e' is replaced by 'o' giving
the name 'ido', 'ito' and 'ato'
respectively. This means that
the halide ligands are named as
ftuorido, chlorido, bromido
and iodido.
• Similarly, cyanide (CN-) may be
namedaseyanidoaccoi:dingt.o
IUPAC2004 ' (i) ne,ative ligands end
;But ih
MODERN'S abc + OF CHEJ.tt
(iv) ·
Theformulafortheco-ordinationenti 'ty, wheth erehargedornot is ~Y, ~
· in square brackets. Polyato~c ligands are encl?se~ in Pare;thencJ~
but all ligands are written without any separation m betwee eses ( ,
(v) There should be no space between the representations of ion~· '
within the formula. ic 8Peciei
(vi) Sometimes abbreviations are us~d for formulae of the .
These abbreviations should. be m lower ~~se and enc}~gand 8
1
parenthesis. For example, PY is used for pyndine and en. is lied l!J
ethane-I 2-diamine or ethylene diamine. Used f01
(vii) The number of cations or ~~ns to be written in the formula is ca}
on the basis that total positive charge must be equal to tota} CU!ated
charge. negative
(viii) When the formula of the charged coordination entity is written .
· t he charge 1s · di cated outside th Without
· m
the formula of the counter 10n,
brackets as a right superscript with the number before the sign square
For example, +or,).
[Ni(NH3)J2+, [Co(CN)6]3-, [CoCI(NH3)6] +, etc.
2
Some common examples are :
[CoCliNH3)4]Cl Cl is cited first than NH3
[Co(~0)2(NH3)4]C~ His cited before N
[Pt CliC6H6N)NH3] Among neutral ligands C5H5N andNH3, C H Np
NHa
5 5 rflcedea
[Ru(NH3)6(N2)]Cl2 NH3 precedes N2
RULES FOR NAMING THE COORDINATION COMPOUNDS
The nomenclature system given by IUPAC (International Union of Pur
and Applied Chemistry) has been given below:• e
1. Order of naming ions
In ionic complexes, the cation is named first and then the an.
(as in NaCl : sodium chloride). · · 10n
Non-ionic complexes are given a one word name . .
2. Naming the coordination entity
In naming the coordination entity, the ligands are named first an.d the
the central metal ion. n
3. Names of ligands
The names ofanionic ligands (organic or inorganic) end in o-. In general if
the anionic ligand name ends in -ide, -ite or-ate, the final 'e' is replaced by\•
giving -ido, -ito and-ato respectively. For inorganic anionic ligands containing
numerical prefixes such as triphosphate enclosing marks () are added. The
names ofpositive ligands end in -ium. The neutral ligands are named as such.
For example, -
in -o :
F- . . fluorido peroxo
Cl- . chlorido
. bromido
~c

,
\,

r,~.111 rt,.
,l •ove
po6:
ti) ~O
NcoMPOUNDS
. ugands end in-ium
tl>'.,,o

+
.
rutrosonium
hydrazinium
Note the spellings of ammme
with two m's. This is uaed only
-
(), +
3 ~o nitronium for NH while all other amines
3
Jt~iJ ugands are named as such are spelled with uaual one m.
' ¾ ,. ) J)e ml methylamine For example, Nl¼Cl¾C~,
'¾ I~ cJl3 2ell Nf4 ethylenediamine or ethane
~ell? 2 , . eth 1 ·amme
~-. ~e-":~--~ · or ethylenediamine
'I~ , ,.., ,tJ,ane-1; 2-diamme should b.iUied .-·, ... --
fh' . m pre,erenoo to ethyl;;,,.
-1, 2-diamine.

(li!l~e . - ·· Abbreviations for ligands should

C5Ils:N pyridine (py) H2NCSmt •••~ thiowea (tu) be in lower case.
@J§Jo
~k' '
. dipyridyl (dipy)
·~I (C61Isll triphenylphosphine
I pll3': phosphme N N In the old system, the ligands
wever, there are a few exceptions tral Iigands.Forexample
°"'). JJ
JJ,O
110 :,:! in namina
(, -" "' · - ··-- · - · · -- - •........_neu
wa, named 'aquo' inold,Yaiom). · ·· · ·····
are named in the order oW) negative
(ii) neutral and (iii) positive. Within
each group of!igands, they are written
r,lll3 nitrosyl in order of increasing complexity,
NO
co carbonyl For example, in the complex,
cs thiocsrbonyl [CoCJ(N0 XN!¼\l+, the ligands .are
named in2 the order : chloro, nitro
4, Order of naming lig~ds
r -~--· l
(negative ligands) and ammine
' WJie~ more than one type of ligands are present, they are named in (neutral ligand). However, IUPAC
~phabeti.cal order of preference without any consideration of charge. For (1971) rules have recoIDlllended that
e¢11Ple, Ul the.complex ~C~Cl(NO2)(NH3)4]+, the ligands are named in the order: all ligands whether negative, ne~tral
aJllllUne, chlondo and mtnt~-N. S~arly, in the complex K;i[Fe(CN)5NO], the or positive be arranged alphabeticsllY
without anY preference order. Some
1>tire ugands are named as cyarudo and mtrosyl. boOks still follow old convention
5, Nunterical pre~es to indicate number of ligands but the new system of DllJllinl
When mo,:e th?,n one ligands of a particular kind are present in the complex, ligands in alphabetical order is
, • the prefixes di-, tn-, tetra-, penta·, hexa·, etc., are used to indicate their number : used in the present test-
·llio~ two,Whenthree,the
four,name
five and sixligand,
of the respectively.
includes the numerical prefix (di, tri,
tetra), then the prefixes bis, tris, tetrakis are used for two, three, four ligands, The name of the complex
respectively. Such ligands are called complex ligands. (Cu(Nli,)4]SO, is :
tAat For example, to indicate two simple ligands such as chloro, bromo, tetraaIDIDinecopper(lll sulphate, .
anunme, oxalate, etc., we use the prefix di but to indicate two complex It may be noted that both 'a',
ligands such as ethylenediamine we use the prefix bis(ethylenediamine) or i.e., last 'a' of tetra and first 'a' of
o!f .,(1, 2-ethan_)_ Th• - • of tlw o,mp!e,< li,.rul i, giv,n in b,aclret,. anunine are to be retained.
~• For example : : tetraalllJllinecopper(II) sulphate
1lin, [Cu(NH3\JS04 : tris(ethane-1,2,-diamine)cobalt(lll) ion REMEMBER
77k [Co(en)sl3+ : dichloridobis(triphenylphosphine)nickel(II)
riitA. [NiC~(PPh3)2l
6. Ending of naJlleS · · .
When the complex is anionic, the name of the central metal atom ends in
-ate. For cationic and neutral complexes, the name of the metal is written
without any characteristic ending, . · · .·
For example, the cationic complex [Co(NH3)~Cls is named without
characteristic ending of the name of the metal as:
[Co(NH,)~Cls : hexaanunmecobalt(lll) chloride . .. . .
The eoordination compound, K[PtCliNHa)l which contaillS the aniomc
complex [PtCl (NH,)J- is named with ending of the name of the metal as :a"·
KLPtC~)) : IM.'taaSiUDl alllJllinepentachloridoplatinate<IV>
siJDUarly, the anionic complex Ca2 [Fe(CN)6] is named as calcium

J,_ is(11)
hexa~errate ·
as tetrathiocyanatocobaltate(ll) ion.
be no for anionic complexes the Latin nam
m co d. For example, ferrate for Fe
Ag, or Au, stannate for Sn, etc.
r
MODERN'S OF C
. . HEJ.11~-
However if the complex is caboruc or neutral the name of ,h q
given as such e.g., iron for Fe, silver for Ag, gold for Au, copper r:r ~e¼l
For example, . 11,
Ka[Fe(CN) ] : potassium hexacyamdoferrate(III)
6
[Fe(CO)5 ) : pentacarbonyliron (0)

7. Oxidation state of central metal io~ .

The oxidation state of the central metal 10n 1s designated b
numeral (such as II, III, NJ in the brackets at the end of the
atom or ion without a gap between the two.
name:,~ no¾
'nelQJ
Let us discuss some examples :
(i) [Cr(NH3)aCH2O)3JCl 3
It may be noted that the gap In this case the ligands are ammine and aqua. The complex is .
should be only between cation ' The oxidation state of ch rommm
chloride is anion. . . III as
1s :•·cat10
. n atld
and anion. The complex part x + 3(0) + 3(0)- 3 = 0 or x = + 3. ',
should be written as one word. Its name is triamminetriaquachromium(III) chloride.
(ii) Ka£Fe(CN)6] : ~'. ·

In this case, the ligands are cyanido. The complex is anionic. Th~ OJtid .
state of iron is +3 as ·· at11ltl
3(+1)+x+6(-1)=0 or x=+3
The name of the complex is P?tass!um hexa'!anid~ferrate(III).
· It may be noted that if the co~plex ·c?ntaining the central ion, Fe3+ .
anionic ' the Latin name of metal IS used
. , '
i.e., ferrate. .; I&
(iii) [Co(~NC~CH2NH2)3liSO4)3 ·,
In this case, ligands are ethane-I, 2-diamine. (or ethylenediamin )
complex is cationic. The oxidation state of cobalt IS +3 as: e · The
[x + 3 x 0]x2 + 3 (-2) = 0 or 2x = +6 . or x = +3 ,.
The name of the complex is tris(ethane-1, 2-diamine)cobait(llh
sulphate. . """J
It may be noted that tris is used because the ligand is complex lig d
(iv) [Ag(NH3) 2l [Ag(CN)2] an ·
In this case, both cation and anion are complexes. The oxidation state
silver in both cationic and anionic complexes is +1. of
The name of the complex is diamminesilver(I) dicyanidoargentateO)
8. Point of attachment
When a ligand can coordinate through more than one atom, then the po.
of attachment of the ligand is indicated by putting the symbol of the
0
/nt
through which coordination occurs after the name of the ligand. Sometun°171
different names ar~ used for alternative mode~ of a~chment. For examp~
NO2- can coordinate through -N or -0. ff 1t coordinates through N it •
called nitrito -N. On the other hand, if it coordinates through O -ON;
it is called nitrito -0. ' '
NO2- (through N) : nitrito - N
ONO- (through 0) : nitrito - 0
Similarly,
SCN- (through S) : . thiocyanato
NCSithrough N) isothiocyanato
For example,
(Co(N02>a<NHa>a1
· (Co(ONOXNHa)JSO, pept.asrnrnfiienlii.
., 9.N---.en- Uieiil ......
Geometr.icsl .
 coMPOUNDS
~,.110N
~pl
jj,111PJe, .
,/ , CI-........_Pt/NHa 4/~~-/J1
c/ .'--NH• .
. dia!ll111ined1chlondoplatmum(II)
aV--~2
Square planar complex
c~- ·JarlY, for o~tahedr~ co~plexes, cis- and trans- are used (discussed
51J!ll. ..,erislll in coordination compounds)
, .
,i.er illr,f jlllling optical isomers
i0·ticailY active compounds are designated by the symbols (+) or d- for
0ProtatofY and(-) or l- for laevorotatory. .
11or eia.mple, .
a-I<s[CrCCz04)3l : Potassium(+) trioxalatochromate(III)
Bridging group~ in bident9:te ligands
For ligands which act as bridge between two metal atoms the Greek
ietter µ (mu) is written before their names. For example, '

r,),c(r-,]~oJ,
In this case, the ligands are~- (amido), NO 2- (nitritQ-N) and NH3
(aJllllUlle). The oxidation state of cobalt is +3 as .
4(0) + X + ( -1) + (-1) + X + 4 (0) + 4 (-1) = 0 '
2x=6orx=+3
Tet;ra.amminecobalt(Ill)-µ- amido-µ-nitrito-N-tetraamminecobalt(Ill)nitrate

(ui,oi.()•OI,oi._]cso 4\ .

• OH .
Tetraaquairon(ID) -µ-dihydroxidotetraaquairon(III) sulphate.

Some more examples are given below:

Name
Formula
K[Ag(CN) ] potassium dicyanidoargentate(l)
'. Complex is2 anionic; therefore, '..'a~ is .used afte~ the ~e or'the·m~tal atom.j
[PtCl(NO,XNH,)JSO, tot,aamminecltloridonitrito-N-platinum(l\l) sulpbato
~[HgC1 ] potassium tetrachloridomercurate(Il)
[CoC½(NO4 XNH ) 1 triamminedichlondonitrito-N-cobalt(Ill)
[CrC~(~O) 2 ]NO3 3 tetraaquadichloridochromium(ID) nitrate
K[PtC1 (NH4)] 3 potassium amminetrichloridoplatinate(Il) .
[Ni(~O)
3 (Nlig\JSO
3 tetraamminediaquanickel(Il) sulphate
2 4
Na[Au(CN) ] sodium dicyanidoaurate(l)
[Cu(~O) (Nlig)
2 ]SO tetraamminediaquacopper(Il) sulphate .
4
. Nag[Co(NO )J 4
2 sodium hexanitrito-N-cobaltate(Dl)
KalFe(CN) 2N01 ~tassium pentacyanidonitrosylferra
Ka[Fe(C O6)J potassium trioulatoferrate(Dl)
2 4
K,.INl<ClllJ /"tl potassium~
fj ..
[Cr<PPbaXCO)i
[{CJ!g)aPlaRhlffl
.......
 / 9118
' : MODERN'$ abc + O
.
In this ca~e, the ligand is 8 complex ligand because it contains the prefix tri in its name. For theseFJi,i;;
~
~ '~
prefixes bis (for two), bis (for three), etc., are used. ~ "
(CoBriCen)2JCI dibromidobis(ethane-1, 2-diamine)cobalt(III) chloride
K'a(Cr(C204)3J potassium trioxalatochroma te (III)
(Ni(C0)4) tetracarbonylnickel(0)
In this case, oxidation state of nickel is 0.
(CoFiCen\JCIO4 bis(ethane-1,2-diamine)difluoridocobalt(III) perchlorate
lNi(dmg)2J bis(dimethylglyoximato) nickel(II)
DMG isiep tive ligand with charge of -1.

/NH'\. la+
[ (en)2 C~ Co (en)
2 bis(ethane-1, 2-diamine)cobalt(III) -µ-hydroxido-µ-
"-oH/ imidobis(ethane-1,2-diamine )cobalt(III) ion
futhis case, the ligands are ethane-I 2-<li~~ (e~) imido(Nli2-f'a nd hy~ ;'o(Olt). The oxidation v"""leOf~
_.ft:-,......,_
te
• +3 as : 2 (0) + x + (-2) + (-1) + x +, 2 (0) = +3 or ,
,s x = +3

[CoClien)2J2SO4 dichloridobis(ethane-1, 2-diamine )cobalt(III) sulphate

~ ~on 's.tate of cobalt ~ouldbec ~ ~~
21, + 2(-1) + 2 (OJI -2= o
[Co~l(e: ; ;~ OJ~ ~ ·- ---.~~.-=~~
·, . . . ,,.
tid~~ -WC?~
2,,.. 4- 2 =o.
:i:~: : : =1, ~~: ~ : :)nitrit; ;: : ~ : : ; ~ :~~~~~
-~---~~7,,-,..~,~~,~77'-~r· :
· or .,.&1!.c 6 , . ;; , . .'.•a iii Q
Na[Co(CO\J sodium tetracarbonylcobaltate (-1)
r • • -- - \ - f':/ ~~,.,..,~~ - - - ·• ·""(• _,.,,.:·~ " _,,_.__, ,.-~ ...............,••_,..,,.........,_ .....,.,..,........,,, , ~ , . . ~ ~·..........--~,......,..,._,,,.,~

9xidation state of Co in this comp~ex is -1 as : +l + x + 4 (Q} = 0 or =,~x_::-, -L . -~

~!PtF6J potassium hexafluoridoplatinate(IV)
!PtBrCI(C5H5NXNH3)J amminebromidochloridopyridineplatinum(II)
~[OsCI5NJ potassium pentachloridonitridoosmateM)
[Fe(C5H5)2J "- - - ·- ~ - bis(cyclopentadienyl)iron(II)
~ca';;~ d is ~tadieny!,..Q6!!a-::J
!PtCI~CH3XNlia)2JCI diamminechlorido(methylamine)platinum(II) chloride
Fe4[Fe(CN)J3 iron(III) hexacyanidoferrate(II)
(Co00Ia)JCIS04 · hexaarnrninecobalt(III) chloridesulphate
Na!PtBrCI(N02XNlia)J sodium amminebromidochloridonitrito-N-platinate(Il}
~(PdCI4J potassium tetrachloridopalladate(Il}
IPtCliC51fsNXNI!a)J a.mminedichlorido(pyridine} platinum(Il}
fVO(acac)2J bis(acetylacetonato)oxovanadium(IV)

pentaarnrnioechrornium(Ill)-µ-hydroxidopen

K,~OH}J
Hg[Co(CNS)J
r
vO°
~01tJ
A'flON COMPOUNDS

ttJSM IN COORDINATION COMPOUNDS

J'0~ or ,n,ore com~ounds having the s~me molecular formula but
'fl!fferent.arran~ement
0
ofatoms are called isomers and the phenomenon .
-j
1 ·G,,ek..,....,,.equa!,ndmero,
means parts.
.,· :
1
ailed 1somensm. ,•
iS ~ause of different arrangement of atoms, isomers differ in one or more
, ·, ~eal or chemical properties.
pli1r:oxners can be. broadly classified into two major categories :
(fSStructural i~omers .<~) Stereoisomers.
,. ,rhese _are further sub-divided as shown below :
·•' . a·:·-> ISOMERISM IN COORDINATION COMPOUNDS
·~ -, ., I
P. -- " '1,I 1
,,>'

Structural isomers Stereoisomers

1. Ionisation isomerism 1. Geometrical isomerism
2. Hydrate isomerism 2. Optical isomerism
3. Coordination isomerism
4. Linkage isomerism
;.. Structural Isomerism ' ':
The isomers which have same molecular formula but different structural
arrangement of at~ms or groups of atoms around the central metal ion are
caJled structural isomers. The'se are discussed below : .
1. Ionisation isomerism · · ·
. The;compounds which have ·same molecular formula but give different
~ns in solution are ·called ionisation isomers, In this type of isomerism,
the difference arises form the interchange of groups within or outside the
coordination entity. This type of isomerism occurs when the counter i~n,, -:_ ,,:-/j'.-~
in a coordination compound is itself a potential ligand. Therefore, these \
jsoroers give different ions in solution. For example, there are two isomers
of the compound of the formula Co(NH3)6BrS04• One of these is ·red-violet ·
and forms a precipitate with BaC½ indicating that sulphate ion is outside
the coordination entity. The second one .is red and does not form precipitate
with BaCl2 but forms a precipitate ofAgBr with silver nitrate indicating ..
that bromide ion is outside the coordination entity. .
The struct~es of the two compound~ and their modes of ionisation ar~ .: , . . -. ,
Structure Mode of ionisation · ,_, •
[CoBr(NH3)JSO4 . - [CoBr(NH3\] 2++ SO4'lr- . ' ( <,
Pentaamminebromido- · Gives test ofSO 42-ions ., I

cobalt (ill) sulphate ·

(Red-violet)
[CoSOiNlla)JBr ·· - [CoSOpIB~{J++Br
Pentearnrninesulphat.o- Gives test of Br ions
cobalt (ID) bromide
(Red) _,, .•
Other compounds showing this type o( isomerism are : . .
(i) [CoC~(NHs>JN02 and [~~¥N02XNlla)4JCl
(ii) [Co(N0 ~)JS04 and [Co(~4XNlia)JN~3 _
8
(iii) WtCit~jJBr2 and [PtBr2<NH,)JC½ .·
(iv) [CoCl{NO~)JCl and [Co~~)JN02 ' - :
2. or Hydrate isomerism _ .. _
have the same molecular {ormul4 but ·
s present as li/Iands (i.e., in the coo •
ules (i.e. present outside the coo • · •
isomers. It is also

In addition to four structural
isomerism, some coordination
complexes exhibit the following
two more isomers.
Coordination position
isomerism. This type of
isomerism is exhibit.ed by bridged
complexes and results from
different placement (attachment)
of ligands. For example,
[ · OH, ] of different metal ions present in the complex.
l<NHa~.eo~H /Co<NHa½Clii
O;;d J
f
ClCNHs),~H)oaraa>,Clj SO,
It is clear that in the two
isomers the ligands amine and
chloro are differently placed
relative to the two cobalt atoms.
PolJmeruatian uomeriam.
This is.not a true isomerism.
It is ua to denotie
rmm,t.betame~~
MODERN'S ab(:+ OF CHE" .
"''SlJly~~
isomerism in case where water is involved as a solvent. Thus, hydrate .
differ in the number of water mo~ecul~s P_re~ent as _lig~n~ or 08 ~::e~
of hydration. This type of isome~s~ 1s similar 1olll8at1on isomens "~•
which water molecules may occur ms1de and outside the coordination Ill, Ill
as a coordinated group or a water of hydration. For example, there ar 5Phere
isomers having the molecular formula CrCl3.6H2 O, These are : e three
[Cr(H2O)6JCJ3, [CrCl(H2O)5)C1:i,H2O and [CrCli~O)4]CI.2~Q
They differ largely from one another in their physical and chellti
properties as illustrated below : CaJ
(i) [Cr(H O) ]CI3 It does not lose water when treated with cone ½
Vi~le: and three chloride ions are precipitated with.AgN~•
(ii) [CrCl(H2o)5]C1:i,H2o It loses one water molecule when treated Wi/h'
Blue green cone. H2 SO 4 and 2CJ- ions are precipit
with AgNO3 • ated
(iii) [CrC1:i(H2o)4)Cl.2H2o It loses two water molecules on treatment with con
Dark green HiSO4 dark green and one CJ- ion is precipitatec.
with AgNO3 • d
Similarly, the following two isomers are hydrate isomers,
[CoCl(en)iCBiO)JCI2 and [CoClien)2)CI.BiO
[CoCI(~O)(NH3 )4]CI2 and [CoCI2(NH3)4]Cl.H2O
[CrCliC5H5N)iH2O)2]Cl and [CrCla(C5H5N)2BiOJ.H2O
3. Coordination isomerism
This type of isomerism occurs in compounds containing both cationic
and anionic entities and the isomers differ in the distribution of ligands in
the coordination entity of cationic and anionic parts. This type of isomerislll
arises from the interchange of ligands between cationic and .anionic entities
so. The examples are :
(i) [Co(NH3) 6l[Cr(CN)6] and [Cr(NH ) )[Co(CN) ]
36 6
(ii) [Cu(NH3)4] [PtC14] and [Pt(NH ) )[CuCl ]
34
4
This type of isomerism is also shown by compounds in which the metal
ion is the same in both cationic and anionic complexes. For example :
(i) [CrOO!a)J[Cr(CN)J and [Cr(CN)lNH3) 4l[Cr(CN) (NH ) J
4 3 2
(ii) (Pt(NH3)4] [PtC14] and [PtCl(NH3)3] [PtCl afils)]
3
4. Linkage isomerism
The compounds which have the same molecular formula but differ in the mode
of attachment of a ligand to the metal atom or ion are called linkage isomers.
This type of isomerism arises in compounds containing ambidentate ligands
i.e, when more than one atom in a unidentate ligand may act as a donor, For
example, in N02- ion, the nitrogen atom as well as the oxygen atom can donat.e
their lone pairs. Thia giv• rise to isomerism. If nitrogen donates its lone pair,
one particular compound will be fotmed. On the other hand, if ozygen donat.es
its lone pair, a diffinnt~(althougb having the same
molecular formula)
is obtained. If the bonding,is N, the pd is named~ nitrilt>-N (or
nitroJ am1 ifit is ~ ~g,;Ju,·gamec1 as IJilrito.Q..,r""~ ;
- 11itriit,.~ rt,;,.~ ~~:r1.t-u
r coMPOUNDS

7
fl/\110N
·l°' NH3
2
•
NH3 2+

' ___ _J __________ ONO I

~3~------.rCo ~ , ,',
veo----::' 1
H~ -..::::.-~-- -- - -- --- ~o,

j~-r-~. :.
. /

NH3
"'"-------+~..:..
NH3
[Co(NH:J 5(NO2)]Cl 2
The nitrite isomers of
[Co(NH ) NO2J2+ were st udied
36
by Jorgensen and Werner who
[Co(NH 3) 5(ONO)]Cl 2
Pentaamminenltrito-N-cobalt (Ill) chloride observed that there are two
rninenitrito-O-cobalt (Ill) chloride
ellow compounds of the same chemical
pen13a111 (Red)
formula having different colours,
already discussed, the unidentate ligands which can bind to the central The red form was thought to be
:~hr ugh two ~nor atoms are also called ambidentate ligands. Other the M-ONO isomer while yelloW
0
r)O leS of such ligands are: . form was M-NO2 isomer. 'J'.he
e$~~N cyanido (through C) - NC isocyanido (through N) red form is oflow stability which
,.,. scN thiocyanato (through S) - NCS isothiocyanato (through N) gets converted to yellow form on
long standing,
:8, stereoisomers
stereoisomers are those isomers which have the same molecular formula
nd chemical bonds but they have different spatial arrangements of atoms.
a1ready ~entio~ed, stereois~me?sm involves two types of isomerism viz.,
eometrical isomensm and optr.cal isomerism. These are discussed below :
g • al . . '
1. Geometric 1somensm
aeometrical isomerism arises in heteroleptic complexes due to ligands
oecuPying different positions around the central ion. The ligands occupy
pasitions either adjacent to one another or opposite to one another. These are
referred to as cu• form (ligands occupy adjacent positions) and trans• form . •
It may be not.eel t.hat in ICl1J81'9
(ligands OCCUPY opposite positions). This type of isomerism is, therefore, also .
planar complexes the poeitiona
referred to as cu-trona isomerism. 1-2, 2-3, 3-4 and 1-4 are cis with
This type of isomerism is very common in coordination compounds. This is
respect t.o each other while the
due to different coordination numbers varying from 2 to 9, commonly enco~~ positions 1-3 and 2-4 are ,rans to
in these compounds. Geometrical isomerism of compounds with coordination
each other,
numbers 4 and 6 is most important and is discussed here.
(I) Geometrical isomerism in complexes of coordination number 4
The complexes having coordination number 4 adopt tetrahedral or square
planar geometry. The geometrical isomerism is not possible in ~t~hedral
complexes. This is l,ecauae in geometry all lhe posilions are
IJ#Va«nl to one an,olhD' in then comple:tes. However, square planar
complexes show geometrical isomerism. ·
(a) Square pianar complexes of the type MA,X.,, MAP, ~X.,, MABXY
, can exist 88 isomerB (Here A and 9 are
neutral ligancls such 88
' H,0, NIia, co, NO, C 11,){ whereas X and Y sre anionic ligands such 88 c1-,
1
N0 -, CN-, SON-, etc.) ,
2
Let us ~ esamples: .
{i) ~ •esiatl in cis and trans forms as : .
-~ ---rHa q _______ /2
_______ ,NHa
I I' I
I I ' -~:
II : ~
I . . ' II
,L.
HaN--------------~
I I · '

a
• (PIO,(Nll,)jl
 MODERN'S atx; + OF CHe
J.11s-r11-,

/"' / /
(ii) [PtCl(C :f\N)2'NHa>l exists in cis and trans form as : ' -~
6
Py-------------·NH3 Py-------------·NH
/"' //3
//Pt~,/
Py-------------- Cl
//Pt~/
Cf----- --------Py Traru•
. • Cu- ) ( s·
1m1'Iar groups (p y)
(Sun~ 1ar grou~ ~y) on opposite positions)
on adJacent pos1t1ons XL h
(iii) Square planar complexes of t~e type s ow ~h:ee isomers
structures of these isomers can be wntten by fwng th e pos~tion of one Ii. 'I'he
(say A) and placing the other ligands B, X '.111d tran~ to It. . , ~and
It may be noted that the fourth structure ID which A IS trans to Lis iden .
to the third.

--7----- X \
ticai

-----7-----,
. B \ ____ _____ B A
/!
I
I
I
\ I
I
I
I
I
I
I

I
I
I
I
I
I
I

7 I
I
I
,'

I
I
I
' \ - - - - - - - • • • •)(

I
I

y:___ \,'
I' M ' I1 M 1 L,' ' M 1 ,'' M '

Bv:___\/
,' I ,' ' ,'

L
I

I B
I

L
!/:___\~ /--------\~
I

II
I I

Ill
I I

IV L
I

Identical
ft may be no~ ~t ~o of these <e:g: ~'.Ian~ ill)~ cis 1md one <e.g. I) is ~
For example, the complex [Pt(NO2 Xpy)(NHpH)(NH3)]+ exists hi thr ..
geometrical isomers as represented below : . . ee

Hf..
,'
----·-:;t0
\ / /
l+ f ~,~\--:7/Nol+ [· ?\·----~·
\Pt/!--,, • +: 1 Pt 1
0

1
NH .
/ Pt /. . / / · \ ,' // ,' - 31
1v~_\,'
Py
I

r-t• - -
I

NH2 0H
• - - • ·- - • ••

(iv) Geometrical isomerism ~ o t occur in complexes of the tY})e·M.\

£(:___ , -~
H N' ---------~HOH
a
.... --,., ~, •• -V,-,• ·... - •, ,~ ·• • • • C .,-
I

• •
2
- • . , _ ....,.. , _ ._ ,. ~ - - --
£(:___
Py'-------~ ·,,
--~H 0H
~ - - ')~ .
' I

2
-,1.

1
MAaJ3 or MAB3 because all possible spatial arrangements for any of th:e
1 complexes will be exactly equivalent.
(v) The squ~re plan; ; colllplexes .c; ntaining ·unsymmet~-bid~ntat
ligands such as [M(AB)2] also show geometrical isomerism. For example the
complex [Pt(gly)2J where gly = ~CH2COO- exists in cis and trans fo~ _e
H2N------------NH2 0 / , ------------ NH2 .

I / !H2
H2C/ / '-. / / '\ C
I / Pt/" / CH2
1 \

""-Pt/ /
, I
• • J .. . • • ,r·.
0-?'C\:J'~------------rc~O
V"' I V"' I
HC~H:~------------~C\
2
I

Cia-diglycinatoplatinum (Il) Trans-diglycinatoplatinum. (Il)

(vi) Geometrical isomerism is also shown by bridged binuclear complexes
of the type MAX4, For example, the complex[PtC12P(CJl6
2
exhibits )sJ
geometrical isomers as :

Cl"-. /Cl'-.. /Cl

Pt Pt .
p/ 'c,/ '-.P(<;H~
(CzH.>a Ci,-fonn ,c
~ NOS
lo~ cOiJ colllpleit [CoC~(NH3)4)+ can exist as cis- and trans- isomers:

, ;.J)edt l + Cl ' ·. l + -

·---+··-··-····· NH ,
~,~<····/1 1~0/./
3
······Cl HN 1·

/ / co~/
f1/.
\

. .•··. \·········..NH3
// 1~
H3N ········--···· ·········••NH .
3
/-···········~H3 [CoCli(NHJJ• Cl
cis· form Trans- form

1~.T ,~le,
, the comPleit (Fe(CN)iNHa)2J- can exist as cis- and trans isomers.

l"'.l:! r
g~_ _
'Tran&
NH 3

[fe(CN),(NH:,),] [Fe(CN) 4 (NHsJ,f

bl octahedral co?1Pl~xes of the type [MA.,B 3] like [Co(NOJa<NH3) 3] also
( ill two geometncal 1.somers. When the three ligands (with same donor
t ) are on the same tnangular face of the octahedron, the isomer is called
or fac isomer. When the three ligands are on the same equatorial plane
J octahedron i.e., around the meridian of the octahedron, the isomer is
111
eridional or mer isomer. In a simple way, in facial isomer, the
,e ligands are at the comers of a triangular face while in meridional isomer,
·,hree ligands are at the three comers of a square plane as shown below:

~· ·$ ·· Geometrical laomerislll 19 11ot

~:
shown by
fac-{somer -~ ' i' mer-Jsomer • Complexes with coordination
number 2 and 8.
• Complexes wi
number
geom

. NWN
.~ . ~ .

,, .. NHs
. mer-
aiste as fac- msr• iaomerL · ·· ·
- MODERN'$ ab<: + OF Ckel.lJ

(c) Octahedral complexes ha~g didentate _ligands of the type M~,:

and M(AA)~ can also exist as cu, and trans isome_rs, ~here AA r (AA)~
a symmetncal bidentate ligand such 88 ethylenedi~e (en),
(ox). For example, an octahedral complex [Co(en)2C½] eJOsts as two . le i(
l+ 1·180rn~
1r"-·/7CI ~7"71\
Cl Tl

oo
~ry,

Len
~f:::,,u'"
eo / ·:; /eo~/j

Cis- (Co(en) CI~•

2
Trans-

(d) Octahedral complexes hav_ing ~ix dif:Cerent ligands of the

M(ABCDEF) would exhibit geometz:i~al isomensm. ~ese isomers tYJ>,
written by fixing a ligand at on~ posit10~ and then placm~ the other 111
Ii ay b,
trans to it. Theoretically, 15 different isomers are possible for suchgazidi
of complexes. The only compound of this type that has been Prep
[Pt(BrXCIXI)(N02XpyXNH3)]. It has been possible to isolate only three ~ed L
forms of this compound. eren1
(e) The octahedral complexes containing unsymmetrical bidentate l'
also show geometrical isomeris~. For example, th: co~pl~x triglycina~
mium (III), [Cr(gly)3], where gly 1s H~C~COO-, exists m cis- and trans. fo
88 shown below : l'lna,
.., . l~o -
H2 ·· · H2C'I .

H/ " . ~7N~H Ht::::::._·· --~·-··7;~H2

/ er/, / / 2
Cr...,........ / CH2

H
NY--f~//{ ·
. /

/LJ.~/~c~· 2

\: / H2c,
cY 'c..:... NH2 ,f-o
if
C~ form Trantr form
C~triglycinatochromium (Ill) Trantrtriglycinatochromium (Ill)

Octahedral complexes of the type~ or M,\B would not show geometrical

isomerism 88 expected. .
There are very large number of other geometrical isomers known but we
have considered only simple examples.
2. Optical isomerism
There are certain substances which can rotate the plane of polarised light,
These are called optically active substances. The isomers which rotate the
plane of polarised light equally but in opposite direction are called optically
active isomers. These are also called enantiomers or enantiomorphs. The
isomer which rotates the plane of polarised light to the right is called demo
rotatory designated as (d) and the one which rotates the plane of polari8ed
light to the left is called laevo rotatory designated as (Z). A 1 : 1 equilibrium
mixture of d and l isomers gives a net zero rotation and is also called race.mic
mmure. The d and l isomers are mirror images of_each other jut.as left
hand is mirror image of the right hand. These mirror images compounds
non-superimposable on each ~ther and do not poaaess the~ ol
These optical isomers also posaesa the property at •
77&e essential condition for a substance to slww
substance should not have o plane of symmet,r_y • •
iaomera have iden~ phJaiad
the6'ection in ~
"The
~ o~poUNDS
J/,r)~ ~110N"es of the type M(AA)3 (where AA is symmetrical bidentate
r . colllPbe
1 [Co(en)l+ and [Cr(ox)ai:3-- exist as optical isomers. Their

1~
118
(I1
J•) sue ., forlllS 11re shown below :
0 Mimll'
~I)" eJld 10.e
13+ Mirror
co
' .•···..•(?1.~~----i
/;'-.I": :
{J/..~L?J en
(dextro) (laevo) (dextro)

() c001 plexes of the type [M(AA)~l or [M(AA)µ (where AA is

~triclll bidentate and X and Y are monodentate ligands) also exhibit
acti\Ti.ty. Some common examples are [CoC~(en)J+, [RhC~(en)2]+, etc. It
oP11 &lt8adY been shown that complex [CoC~(en)2]+ forms geometrical isomers
d trans form). It is interesting t.o note that the trans form does not show
:Z
(ciS isomerism i.e., it cannot be resolved int.o optical isomers. The reason is
oP1t the lllolecule has a plane of symmetry. On the other hand, the cis-isomer
t~syOlnletrical and can be resolved int.o optical isomers.
Cl
Cl
T
CI TMlnor . Ct T.

Cl
U?NJ
rrans{CoCla(en)J- l8om8r (opticallY JnacllV8)
Cl
(dextrO)

(Non s ~ e rn1rror magesl

(188YO)
c/S{CoCl2(an)2J+ isOll18r (optlc8l'Y acttve)

<~

""=L··?,"\ r· .
rnnor lmag88) .

•~ :,;-~1=
similarly, the coordination entity, [PtC~(en)2] 2+ forms cis- and trans-

t::r,~
;-q/1 f/;).<Jj
'V----t---,
de-

. . 12+
- I
I
I
I
I

:
I
REMEMBER

i(J-.y .1
I
I
I
I
I

3~
, pt~ , I
I
I
I
I
I
I
I

d8-IIOlllll'II
opllcallylCIMI
 MODERN'S 11bc + OF C
11~,s-r
(iii) Complexes of the type [M(A:\)~ Y..zl containing one 8Yto. lly~~,
bidentate ligand show optical isomensm. !<'or example ICoCii(en)(llletl'i~

r
exists in d- and 1- forms.

7+ .
Mirr
~ ) ]•
i

~1/NH,, ""[>~~ r
• NHa l or

I -----P.lJ"
1

Cl

Cl Cl
(dextro) (laevo)

(iv) Octahedral complexes containing hexadentate ligand

ethylenediaminetetracetato (~D~A) also show optical isomerism. Fo: esuch as

~\1-c~~ r
[Co(edta)J- exists as two optical isomers. lCan:ipJe,

Mi~r :~-to r
.t/1\
o(._: ---~-~~-~ I/

\.,1" /
2 \H~CH (
l °"c /;c'H2 ct{""N"--- ·--------~
/c~ CHZ Co,. . . . . -/
I \."-cl',.,,
2

0 - - • · --NY I
'-. CH')
2 ·-0 ·
,<; cH2 \ c/
I
Of cl
o-
CH2
\;
II

l'O
0
(dextro) O i
(laevo)
Optical isomers of [Co(edta)]-

Optical isomerism in complexes of coordination number

Tetrahedral complexes are expected to exhibit optical isomerism4b
there is no plane of symmetry in their molecules. However, it has n ~c:use
possible to isolate optically active tetrahedral compounds when all t~ tn
ligands are different. However, tetrahedral ligands with unsymm _our
bidenta~ lig~ds s~ch as 1Ni(CH2NH2C00)2] i.e., bis (glycinato) nic:e~;~l
show optical 1somensm as : l
Mirror

/.) II c~NI/)
/~N :'
'
I
N , •
( N / glycinate ion
represents

:,OLVED

xists as cis-trans forms as :

NC
NH
3

CN
i-

NC"'---+---"'.
NH3
trans-

.• d