Coordination opaund

h nn campunds Containtng a centaa metal atam

9
oY on aumundes byanumb\en o p a t e l chaged
Lon 0Y neutral malelasmare than ifs norma

10 valonca

Centar metr atom fe 0umundad buy six CN

Lon

Sh etan tnair peperttey n asl d and asutam s l e but

r pmpestés oani entie dellerant fon ihs tonekihuaud cont.
Jhe etain their Ldentihy in the i d s t a t e , ewen
athay Soluent
Wat
k[FelwJ +[fel
auble salta
formod
Iheso a e stall addi bium tompounds om a mixhu
o wo Satuated idmmpound She eau up thto
whin-- d'ecolved inL0ater
wattr feet NHet 2
egi fesa, CNH) $0 S0l
Mahr salt
k,80 ALS 24 HaoPatash alum)
 Codxdena twn Conpounds
8

h a s enst in Aeld state

and decocwertetnto tonu
saAUell as in 0outdn.
magusbssoaTin:.

10

2 hy ane formed fpom Jhey ano omad fom

11 Ainplelalba ,with may Aalta mxed m.eguemalar
ma n t ho ixed -pop N om thesr
12 eumalar proportn otitons

3 he Chnplex n tnsttt o hCstsk of _iande

LArdnate hmd behuresin
2 the

y cenba metal atom homekal con exhhE.

Lthiht_me than its thet neTmalalonua
nenalL valent
5

Jher_pepert anL Aam

6 th Conslhuontf as thase f -hir constithents.

A La0dinahin ompnAd h nldnuoabdle _pant

d nm- io ni
Lalil p a n t h A endral metal aom
Lm bmde
to a ied n o
' My
ppacitelu eharse
me uley eesëntedAuthin
A4uaAL hracu n tonshalA
naine eson Co0dnatn Sphdye
tomplexton Caordunatm entih-
 Coordtratin mmber-
Contrl 3 e 3e wndtntn)
meta
Lmicale
0

7tgand(union iabfe
Canplexlon7Coordnatin phere
2

She cmkaalslo pantia oitten outtrdo tho barncuots

calledas

pe LAdinatan sphans
:Li) Caton' complex -_A emplex in uheh the complex ian
Caxiesa net pocitive charre.
2+
ColNH)31 e -

i Animic Complex_ A Lpplex in clh tho Ce ex Sunday22

Lm cane a net megatzve_charse
A (cja fe lca,
i) N e t a omplex_ Acplex Camyan no net charg
charse
gNcaJLC(lHs},elete
h e dene tbms uhiche
Liandsi donate a p a o eleconu e themetrl abn
Cadinate hnmd wth it
anp tello d_ ugand
Lipends ane lon haans, meln ows aods
 18 25 26 27 28 29 30 29

Jhe no- codinatng gathg-

ups pereat n a pad callod thedeatidky o tha
8 and

Jhe donr ane Calod _co8rdinat nS

Coxdinatron runbtr-he total no-

10 ands
i eallad the
attaehc ba centaalL metalatbm 0x tom
11- Condinabn nALmber t h a t ab or tm
0R
2t defthad as temoe Condinate bomds tor ned
bythLisand. thab metal am 0r ion
B m the h a . e p a i r dmated the ligards
Ans ans e flandtng pes
aUdonae Modenate Lisand Lahch can
Cedinate t me cemhal metal aom r lm thngn
tau dne dmOT at

N e t a l untdetate and chanez20

H
NH
CO Caxoe CS thiocarbon amineR

ND
methamine GH) MH dimethLamne
Pyri d'ne

CaN trigthpa PH-pho

sphine P)

LCGnsP ir phenyLphasphi nez

0'
27 31 25 26 27 28 29 30 31

udeta te
Anon as ands change-V.
H
F
dr'do
flsro. /fuond CH ey clapentadieny
C choro Cgt aeehglace onato
bro mo bomdo -acac
to do /od do
OXo oxt ddo
-tH=C-Ch
OH hadoxd d r o xi'do
CN Cy dolcyona, a t s amhtdentate
NC ands
coc anid
H
hidohido
hdidL HS mercaptD
So ulphato So Aulphito
thiosulphato
Cayoonato NH amdp N ntrido
NO nitrmtp NH2 Tmido
NO, aztdlo
nitritD-N
(or t r )
N
abidentate
0NO nitrito -0

SCN E thioanao -S amidentate

NCC thto aiato N_otocana.to
CHtor atetab ethox0

Bcdertade Didentate Lgands a Jhes a uqands

h th have hoo dpnoratnMA codimate "w th the
Cent metal abm ato Ln a t tun posttonA

e etglenediamine Len)/ Ethane -,2-anine

CHa-NH
1
Chang =0

H-NH
 17
16 11 12 13 14 15 16 24 19
WEDNESDAY 22 23
(G.O 17
18
18 19 20 21
25 26 27 28 29 30

e 0Xalate i om ¢00 7 d h a r= -2
(ox) Co0 name Oxalat
8

- 1

9 si'nate ton( CH-NH change

nane- 9yctnato
Cod
10

11 d'methLgyaxinate ,dmg chaag

Chz-C=NOH
12

en dimetkggaxmato
o rmlEtidontnte.

C) Pddent ate sands dhesansugandshaving

2
Mono than tuo donor
aoms Mthoir meloulos
3 to codinate wth Hhe
metul atm L'an
4

i datate hands hooan u'gands wth

6
or terdantate lgands three danar otonu b
Coydinateunth tho _eendal
7
metal atom LOn
e olethsnetrianintdren- HNCHCnNH)
7
NH
>M
H
 S Wk M T W T F Week 22

26
M
2 3 4 5 S S
23 1 2 Day (146-219)
467 8 9 10 11 12 284 5 6 7 8 9 10
25 13 14 15 16 17 18 19 29 11 12
76 20 21 22 23 24 25 26 30 18 19
13 14 15
20 21 22
16 17
23
THURSDAY
30 24
27 27 28 29 31 25 26 27 28 29 30 31

ldetradentat nds Jhese an gands tk

four doDY atom t co0du'nate wth fhe metal atom

e e thyltetramine (trien )/trientine.

Fmula CH, NH CHCH NH
H
N
N
4C CH
M
CH
H
N
H

H,C CH

t Petadentate Lsaads he ant utands uith ive

den n atoma o coordinate ut tho tena metl_atom

- Ethlemedi'ami'ne trtacetate
M ton
N
H
 26
27 2 28 2 28 29 30 31

D letndentatee ends Jh ane Lgands oth

ou dondr atomu Co0rdu'nate wh tho metal atom

e Te tlletramine (trien )/trientine

10

Faula CH, NH CH CH NH
N
2
N
CH
M
H. CH
A
H H

H,C CH

lDYemtadentate Lands h ane uigands unthhve

denn atoms to co0rdinate utt tho Lendametl apm
Lon
Ealenedi'aminetriacetatte
M ton
HC
H
CH
H
 17 18 19 20 22 23 24 25 26 27 28 29
28 29 30
18 25 26 27

lv Hexa dentate hepe an cyands

wth
n th otr dinor atma to loordi'nate wtth the central
8 metalatom
Elenediaminetetraacetate Lonedta)
chaage= -4
10
N

1 CH, C0o

AMbidentate hand Jko^e ano

the
manadentate
central atdm
Lisands hich c å n Loxdinate_wrth
thiugh mene than m te

eg-M and_M 0 -N 0

tnn N M-meta
M S CaL and M. NCS
5

thiscyana teofhdCanato
6
tho0 anato- N

M CN MG NC
Canido Tto CaM do
 26 2/ 28 29 30 31

Chelation Brdeutate and padentate 2ands attach

rel o he centaoal mtta ahm
0
Memblred
dma abmJ
ring wt h
T the cental'atmor Cn.Such
aands an calldL cheattng'gands_Iha ring
tcalra che tate and
10

Callea a chelatin thimbpeaty

11

Chalatng gads AcabrWas a Lomplex than the uLntdantate

onalegs"cledo4 cheting elect
0xdain_state t 0xdatin ne an element d a conplex
Jh oxtdatam e-e thL Centra_atm u defnad a the
Char it_caxr aCalulated asM ndna
apria te charze to the 'gands b and u l g tha
ALm t h charfes temtxal aLma and the
gands efu to Ai Charg0N ocaodinatin.Sphan
E epesaded Koma umbtr ii payentha seu aftar
thamamiothe centaa alom has Sunday 29
Cayyelaon Lo0rdinatin mumbe.

Char on -2
NHnuhraigend) = _o

=t2

we Orite it as C I1)
 MONDAAY 21 16 17 18 19
17 18 19 20 21 22 23 24 22 23 24 25 26 2 2 2
26 27 28 29 30
18 25

8
Fe1
9

Cbdinattm nd Fe
10

0N N i
NCa
11-

12 Ni(0
0' Co on

3 Coad i n a n no Cou)
2

Fe KLEGb4)J
5

= +3 Fe(11
Condnatinno
nd n t 3

Coardi'nattin no CA_datminod y hne, ofima

bondsfpomed b the Lizands untththo Cdra ahm
Th i a htnd
b t d aM £pressnteo a p a i r af duts
pyece eAng th don atdm HheLgand' dn h
oxma f boRdA ano
eg [Co NMs),13t
 20 21 22 23
27 27 28 29 30 31 25 26 27 28 29 30 31

ofLrodinatzun Campands -
LUPAC nomentlann
3

Ruley
hecat hathaaainple Cnplex u
be wnHea r n t L l o d by he 0-nad
10
omala o he Co_rdinatin ophenr whsthen
2
11-
n e a dr ehanga d L4 wntain Lsuana bracuet.

03) t h i n dhe pmbol

the oddinatriin phean he
metlatom u tnten fixt tloued b the Smbols/
oxmaus o gandsanangod alplha beticallu
accding their namesiapectie ef hha
change prAnt_on thon

Jhe name otheComplex tA wnitten as dn Aa>d

Statm with aAmall t t e r [lower Cane

SSFhe farmuula e mth Cmplex iana fo he tonlen-

5 Lthant Lanihnag thaeanton' tm h chanqes ha
plex wnlen ttsidu thaA9uans bauot
6 anu'ght p e r cercpt with th ben flnued hi

LJfrAnbidentate ands the point of atlachment f tha

Ligand CA deninated_ plaeing
olansy_atm attached len Hha nam he
nepaaateA byhyphea.
) 9P hen an At ands he aame pe tho
rehixes d tri eapeada jeke i uaad
 22 23 24 25 26 27 28 29 27 27 28 29 30

ou H/4omoltunls ands, both

8 a te, a a and f t a
aguaamni ne dhe to be natainad
9

h o n a a poly dontate Ltgand inndas a nuumbtn, }

10
ddepyricdi 0Y thano cuamine bts, trt
Then
pentakie hexakt8 t . aa wandL
11 nAterd o A r i - e t a -ek. and th nam
h placadLothinL bxaleotc uithaut
kphens.
12
aa

ttmas dirmsthlam.ine tdheh ts a

2- dlenant Carnpound

IheIh name4 h jands Onl oriHen alphabe tically

Uaedby fh mame tho_metal atom/ton 0hile
4

dnHeg a t ' . Sho preferes d t i jebaek

5- an nt haeanstdered hile datarmundng
th alpha be t a l Oder.

eg LPt (NH),cl (no,)So

tetraammine.chodonitnplatnumliv)aulphate
oxidabnc t a e aom
o man mum ber- wtthn pananthasr at
end
e nd of h motal atom t t h a t o
fuwo(catone conp la x)
Oxtdatin stae of NE in k nilN) 0
Co
U_fostbive 'gands end intian
8

y 3th CarplexLon tA annittha name he

9 centr atim ends in-ate follaed by th
oxidaton nmben tn ackets
10
the Corplex o au'dte, Caton ce Ht ,tho
11 hame he metn ends tn -te fLued b, tha
atd
12

e Pt (NHa) cl damminetetra chlordaplatinumv

Na [AL F Sadium hexafuoridoauminate(1n)
[Ni ldmg)1 isldinthlgtyaximath) nirallu)
HLPtlen hexacasanaplatincu) aid
aud)

asieunddentete Lgands
No.t t m Sonium

NO nitmntum

NHNH dazinium
 20
wnit AFRIDAY 21 22
21 16 17 18 19 20 28 27 28 29
Names 0 22 23 24 25 26 27 29 27

Cooydinmatton compaunds tmtainng

Catinic corplex ton
8
C o lnlH Cl hexa amminecobaltln) chla rida
9

LCrH,o )y ci, No tetraapua diehlaidochrmumu) tat

10

12 tetaammine_chlorldsntmcabalt (11) ntoate

ehdanediamine
Cle)g Elyris lgea:
chmm'um1) chlomde
ethae -dsane

5 Co Ci,len),o dichlortds bis cohalt (iv) Sulphate

tetmammineagua bm m'do.cabalt(in) nitata.

LCtLlen), lONO chlaridnbislehane-1, 2- d amdn)

hexaamminecsbalt(m) Cond
ulphate

H s ) P , L t r Ltaahtamlphntphine)Thadiuml)
chundu
31 25 26 27 36 29 30 31

Codxdu'nahin uMpsunds caing aniane tanplex Lon

patatsium hexacyanfexrate(11)
9

NaNaLCo (ca) No] Srdalumpentaeanani tmcyLabaltate

10
(Iu)

a f e C 0 4 ) , 7 Sadium ti.axalatakerate(u).
12

H LCaNCe) mertny tetra itothiocanato ca hal tate lu)

2 m uy tetra thibtyanatn - N- abaltate (u)

s) bmminetachlmidoplat'nate ()

KyLNilai), potas Cium tetbazaionickalate (o)

Sunday 05

feFelen ferntc heaganoterraten)_ 2+

+3+3 +3x-L 0
Dxidator ehWe x
3 - L 20
oFe X t2

t
Li LALH :8iun tehdaida alumi nate lu)
1) Na, sif,] Sodium hexat urdosilicateliv)

1ola LNi ed Sod ethsasdiaminate haacelhbnu'alade()

 21 16 17 18 19 20
27 28 29 27 27 28 29 30
23 24 25 26
22
Nn-tonC dmabn Cmptnandz

N:(t0), tebtratarbmgLnceusl(o)
Mn,MnCa)n
10
dadeeatayhairimangar
Nt (dm) btsdmath yoxtmata)ntiualty
2

pentacahotrphenphosphonackomiu
CrtPPh t

Clsy) dsyeinah tipptrlu)

tramhetrindtnabaltLy

felchs bislelapenta-denyLmnu
31 25 2b 2/ 28 29 30 31 29 30 31

Cordinatn campnunds cmtaing amplex Catainad an

Cond
'

10

ttraammintdt thlo ridoplatinumv) te.trachlanidaplatrinate (1;

3
Cxai
tttammi nedichlaridocabalt (uL) hexacyannchomate (u

AgAy drammaunesilverU diagahdo argentafe(y

)P d1 ttmpjidinaplat.hunluplattanateIy
trachlaida-
 W muula o a Camplex when thenam d rn
8

whthe catm o as behaves

9 adital
9
0xrdatin
o echasgp m h mplux an the Dm d th
10 h aoho matrl atom ond the tal changeamied
b dh Lgands
1rnha thari lodatan otnk oa madal abm taludays tv
C a ms Can be ca ated'
12 uultiping Dmua Catnar anu dn b
a Auitn onaanantoo ths Hha_changos be t m eqal

es tehaamminea4ua.chlarido tahalt n)_chlanide

cohalt tE charge a ma qandy

3+D+D+ (-1)
Cange on m cl e -1 Sunday 12

H),)L c

2 S odium penutiana ntmylnulphdsfe peatelu_

= 3+ (-st0 (-2)

ChangoOn 0n nodum ct
NayLfelcan)Na) (S)
 21 16 17 18 19 20 21 22 26 20 21 22 23 24 25 26
22 23 24 25 26 27 28 29 27 27 28 29 30
3 patatst tedhadnxozintadsLy
8

Chanpe n bm st|
10

11

12 hxaaquatmnliy qulphae
1

2 Change on One Alphate = - 2

Spota.tkiu teha.ciyana hcualakeluy k'

2

chlando nim daeninda plathumluy

5

62pota fum hexacaeansttnatemy

bia laehyLaretonata) ixtdoVonadi'umli
y lacac 0
CLordda-bt (ethlens dda mna nh crhallut n

)pentaommine nitito-0-uhalteuLCo LaND)]2

Lon
5. Isomerism in Coordination
Compounds
the same formula but
molecular
Two or more than two compounds having diffe
is called isoe
arrangement of atoms are called isomers
and the phenomenon

Coordination Compounds
isomerism.
Isomerism in

Structural isomerism

Coordination| Coordination
Ionisation position isomerism*
isomerism isomerism
Hydrate Linkage Polymerisation
isomerism isomerism isomerism*

Stereoisomerism

Optical isomerism
Geometrical isomerism
have molecular formulae
Structural lsomerism: The
isomers which same
() of atoms or groups of atoms around the
but different structural arrangement
structural isomers.
central metal ion are called
same molecular formula
Ionisation Isomerism: The compounds which have
(a) are called ionisation
isomers. Ilhis
but give different ions in solution between
when there is an interchange of groups
type of isomerism occurs sphere.
coordination sphere of the metal ion and the ions outside this

[Co(NH),(SO,)]Br [Co(NH),Br]SO,
PentaamminebromidocobaltlI)

Pentaamminesulphato
cobalt(IIT) bromide (Red) sulphate (Reddish-violet)
B r i o n inside coordination sphere
SO ion inside coordination
sphere and Br" ion outside it. and SO ion outside it.
Mode of ionisation Mode of ionisation

Co(NH)s(SO)]Br [Co(NH5Br]SO,
[Co(NH),(S0,)I*+ Br [Co(NH),Br]*+ sO
witn
Gives yellow precipitate with Gives white precipitatev

AgNOg, i.e., gives test for test for

BaCl2, i.e., gives
Br ion. SO ion.
Outside the coordination sphere

[Pt(NH),Cl]Br, [Pt(NH Br,]Cl,

Inside the coordination sphere
 Ch) Solvate or Hydrate Isomerism: The compounds which have the same
molecular formula but differ by whether or not a solvent molecule 1s
directly bonded to the metal ion or merely present as a free solvent
in the crystal lattice are called solvate isomers. The phenomenon molecule
is also
known as hydrate isomerism in case the solvent involved is Water.
Hydrate isomers differ in the number of water molecules present as ligands
or as molecules of hydration.
For example, CrCl3.6H,0 has the following three isomers:
ICr(H,0)%lCl :Violet (anhydrous)-It does not lose water
when treated with conc. H,SO, and 3CI ions
are precipitated with AgNO
[Cr(H,0),CIjCl2.H,0: Light green (Monohydrate)-Itloses one water
molecule when treated with conc. HoS0, and
2C1 ions are precipitated with AgNO3.
[CrH,O)CI.2H,0 Dark green (dihydrate)-It loses two water
molecules when treated with conc. HSO, and
one Cl ion is precipitated with AgNO3

( Coordination Isomerism:This type of isomerism arises from the interchange

of ligands between cationic and anionic entities of different metal ions
ions present in the
present in the complex. This arises only if the metal
cationic and anionic entities have same coordination number and charge.

For example,
[Co(NH)l [Cr(CN)] and [Cr(NHl [Co(CN)s]
[Cu(NH)J PtCl) and [Pt(NH)J [CuCl]
which have the same molecular formula
L Linkage Isomerism: The compounds
to the metal atom or 1on are
but differ in the mode of attachment ofa ligand
are called ambident ligands.
called linkage isomers. Such ligands
For examnple,
and [Co(NH)NO,]Cl2
ICo(NH,ONO)JCl% Pentaamminenitrito-N.
Pentaamminenitrito-0.

cobalt(IIT chloride
cobalt(I1T) chloride

(Red) (Yellow)
and [Mn(CO)(NCS)J*
(Mn(CO),(SCN)I
Pentacarbonyl
Pentacarbonyl
thiocyanato-N.
thiocyanato-S-
manganese (II) ion
manganese (I) ion
are those isomers which have the same position
(ti) Stereoisomers: Stereoisomers around the
they differ in the spatial arrangements
of atoms or groups but
central atom.
Geometrical isomerism arises in hetroleptic
(a) Geometrical somerism.:
difterent positions around the central
complexes due to ligands occupying
either adjacent to one another or opposite
ion. The ligands occupy positions
to one another. These are referred to as cis-form (ligands occupy adiad
adjacent
positions) and trans-form (ligands occupy oppos1te poSltions). This type of
isomerism is, therefore, also referred to as cis-trans isomerism. Geometrin
al
isomerism of compounds with coordination numbers 4 and 6 is the mos
important.
Geometrical Isomerism in Complexes of Coordination Number
(Square Planar Complexes): The complexes having coordination on
number 4 adopt tetrahedral or square planar geometry. Geometrical
isomerism is not possible in tetrahedral complexes. This is because:in
complexes with tetrahedral geometry, all the positions are adjacent to
one another. However, square planar complexes show geometrical
isomerism.

For example.
[PtClNH),] exists in cis and trans forms as

C .NH3 C NH3

CL NH3 NH
cis trans
(pale yellow) (dark yellow)
PtC(NHld

Pt(gly)] where the ligand gly is NH,CH,CO0 (glycinato). It can

exist as cis- and trans-isomers.

HC-HN- - -- - - NH-CH

-O NH-CH2

HC-HN--
O cis trans
Pt(glyl

Geometrical Isomerism in Complexes of Coordination Number

(OctahedralComplexes):
1Co(NH),Cl,J' can exists as cis- and trans- isomers.

CI C
HN CI
H,N- -NH

H,N NH HN

NH3 CI
cis trans
(violet) (Co(NH,,Cld (green)
 .Pt (NH)2C1,Br>] can exist as cis and trans isomers.
CI
CI
Brx CI
HgN- Br

Brk NH3 Br .NH

NH3 CI
Cis Pt(NH,),ClhBr) trans

(b) Optical Isomerism: A coordination compound, which can rotate the plane
polarised light is said to be optically active. The coordination compounds
which have the same formula but differ in their abilities to rotate directions of
plane polarised light re said to exhibit optical isomerism and the molecules
are optical isomers/The optical isomers are the pair of molecules which are
non-superimposable on the mirror images of each other. These are called
enantiomorphs |The isomer which rotates the plane polarised light to the
rightis called designated by (d) and the one which rotates the
dextrorotatory,
plane polarised light to the left is called laevorotatory, designated ().
as

rotation and is
An equimolar mixture of 'd' and " isomers gives a net zero
also called racemic mixture.
active is that the
The essential requirement for a substance to be optically
structure. The most
substance should not have a plane of symmetry in its
isomerism are the
common example of complexes showing optical
octahedral complexes having bidentate ligands. For example,
of the type [M\AA)a where
Complexes of the Type [MAA)a: Complexes central metal atom,
to the
AA is a symmetrical bidentate ligand coordinated
exist as optical isomers.
M For example, [Co(en)al" and [Cr(o*)31
3+
en

en Co

en-
Mirror form
d-form
to bidentate ethane-1,2-diamine ligand
Fig.9.5: Optically active forms of [Co(en)*", where (en) refers

Ox OX

OX
OX

OX
OX
d-form Mirror form
Fig.9.6: Optically active forms of [Cr(ox),l, where (ox) refers to bidentate oxalato ligand
Complexes The complexes
of the Type [M(AA)A2)ligands, es in
which
wh
AA and
chelating two two
symmetrical bidentate monodenate
to the central metal atom, M, also pvhate
ligands, a are coordinated bit the
DIt the
isomerism and can be resolved into +
phenomenon of optical optical
isomers.
An example of this type of complex 1s
[CoCl%(en)2]*. It exhihis
geometrical as well as optical i8omerism. Its cis-form is unsvmmot
while the trans-form 18 symmetrical because it contains a nla
symmetry. Hence, optical by cis-form onl
isomerism is shown ot
d-and 1-forms. The d. and 1.f Cs
form has been resolved into along
with the optically inactive trans-form are shown in Fig. 9.7.

en CI

Co en

m Mirror forr Optically inactive

cis cis trans form

Optically active cis-forms

Fig. 9.7: Optically active (cis) and optically inactive (trans) forms of the complex [CoCl(en)]

Complexes of the Type [M(AA),ab]"*: In this case AA are symmetrical

bidentate chelating ligands, while a andb are monodentate ligands. Such
complexes exist in three forms, two are optically active (d-and 1-forms)
and the third one is the inactive meso form. An example of this type of
complex is [CoCl(en),(NH)]°". Its three forms are shown in Fig. 9.8.

NH3 NH3 NH
ACI|
Co en en i
Co

I d-form
cis
Mirror form
C
Optically inactive
cis meso form

Fig. 9.8: Optically active and forms of the

meso
complex [CoCI(en)>(NHs)
Notes
ctahedral complexes containing hexadentate ligands such as
e, [Coenl
ethylenediaminetetraacetatocobaltate(III) ion, also
18omerism. show optical
An of complexes
case with square planar
coordination number 4, squar
complexes do not show lane
optical isomerism because they c o n t a i n a plan
of
symmetry but tetrahedral etrica
bidentate ligands complexes containing unsymme
such
netrical

nickel((I), show
as
[Ni(CH,NH,COO)],
optical isomerism i.e., bisE
ycinato)

as shown on next page

6.
Bonding in Coordination Compounds
AWerner's Coordination Theory
T1823, Alfred Werner put forward his famous
formation and structures of theory of coordination to explain the
complex compounds. In recognition of his work in this
feld, he was awarded the Nobel Prize in
Chemistry. Werner is thus, rightly called the
Father of Coordination Chemistry.
() Postulates of Werner's Coordination Theory
(a In coordination compounds, metal atoms exhibit two types of valencies,
viz., the primary:dáteñcy arid thé secondary valency.
The primary valency is ionisable whereas the
ionisable.
secondary valency is non-

K,[Fe(CN)] 4K"+[Fe(CN)1
[Pt(NH)]CL [Pt{NH* +4 CI
In modern terminology( the primary valency corresponds to oxidation
state and the secondary valency to coordination number. For example, in
[Co(NH)1Cl3, primary valency of Co is three and secondary valency is six.
6) Every metal atom has a fixed number of secondary valencies, i.e., it has a
fixed coordination number.
c) The metal atom tends to satisfy both its primary as well as secondary
valencies. Primary valencies are satisfied by negative ions whereas
secondary valencies are satisfied either by negative ions or by neutral
molecules. In certain cases, a negative ion may satisfy both types of
valencies. For example,
I n [Co (NH3).]Cl3, six NH, ligands satisfy secondary valencies while
three CI counter ions satisty primary valencies.
n [Co"NH),(H,0),Js0, four NH, ligands and two H,O ligands satisy
secondary valencies and one S04 counter ions satisfy primary valency.

(d) The secondary valencies are always directed towards the fixed position in
space, i.e., they are directional and this leads to a definite geometry of the
coordination compoundfThis is responsible for the isomerism in complexes.
For example, if a metafion has six secondary valencies then these are
arranged octahedrally around the central metal ion. If the metal ion has
four secondary valencies then these are arranged in either tetrahedral or
square planar arrangement around the central metal ion. The secondary
valencies, thus, determine the stereochemistry of the complex.
On the other hand, the primary valency is non-directional.
 many different coordination
(ii) Werner prepared and isolated
com.

below:
nds frorm
CoCl, and NH2 which are given
(a) CoCl.6NH: [Co (NH3s]Cl (Orange-yellow)
[Co (NH,), CIJCl2 (Violet)
(6) CoClg.5NH
(c) CoClg.4NH3 Co NH), CI,]CI (Violet)
(d) CoCl3NH, ICo (NH)3 Clal (Green)
(iii) Werner's Representation: Consider the case of CoClg. * NH, where
maxi
value of r= C.N. of Co(III) =
6 and minimum value of r= C.N.- ONmm
. =3.
Table 9.7: Werner's Coordination Compounds

S.No. Werner Modern Tonisation Secondary Primary

Complex Notation Valency Valency
Satisfied by Satisfied by
1. CoCly.6NH Co(NHlCl Co(NHl3 + 3CI Six (NH3 Three (CI)
CoCl.5NH, CoNH),C)C, |[Co(NH),CI)**+ 2C1 Five (NH1 Three (CI)
and one (CH including one
(CI) with dual
nature.
CoCl,.4NH, ICoNH),CljCi [Co(NHy,Ci"+C Four (NH Three (C)
and two (CI) including two
(CH with dual
nature.

CoClg.3NH Co(NH),Cl [Co(NH)Cl3l Three (NH | Three (C) and

(Do not ionise) and three all with dual
(CI) nature.

From Table 9.7, it is clear that the electrolytic conduction of the complexes will
bein the order 4< 3<2<1.

NH3 CI

HN NH3 NH
Cl-----
HN
C -Cl
,
.
HN NH HN NH
NH3 NH3
C (i)
C
HN NH
Cl-- HN NH

H,N NH CI
CI
(iii) NH3
(only CI ions joined by (Tv)
Fig. 9.9: Werner's (----) will ionise).
representation of different andNH
complexes prepared from
Valence
Bond Theory (VBT)
B theory was proposed by Linus
Pauling and describes the bonding in terms of
This orbitals of the central metal atom or ion. The theory mainly eals with the
hybridised
metry
ometry (i.e., sha
shape) and magnetic properties of the complexes.
Postulates of Valence Bond Theory
a) The metal M loses requisite number of electrons to form cation. Number ot
electrons lost corresponds to the oxidation number of the metal ion.
(b) The central metal atom or ion in the complex provides a number of vacant
orbitals (equal to its coordination number) in order to accommodate the
electrons donated by ligands. Each monodentate ligand donates a pair of
electrons to the central metal atom or ion.
(c)The vacant atomic orbitals (s, p or d) of the metal ion hybridise to form
hybrid orbitals , with directional properties. These hybrid orbitals now
overlap withthe,ligaDd orbitals to form strong chemical bonds.
The d orbitals involved in the hybridisation may be either inner (n -1)d
orbitals or outer nd orbitals. If inner d orbital is involved in hybridisation,
it is called inner d orbital complex as in [Fe(CN)]* in which
hybridisation of the central metal ion is d'sp" and if outer d orbital iss
involved then it is called outer d orbital complex as in [Fe(H,0)1*" in
which hybridisation of the central metal ion is sp'd".
e) The complex with many unpaired electrons is called a high spin complex
and that with paired electrons or with one or two unpaired electrons is
called a low spin complex.
6 A covalent bond is formed by the overlap of a vacant hybridised metal
orbital and a filled orbital of the ligand. This bond is also sometimes called
a coordinate bond.
(g) If the complex contains unpaired electrons, it is paramagnetic in nature
while if it contains paired electrons, it is diamagnetic in nature.

VN(N+2) B.M.
Magnetic moment =
Bohr Ma
Here Nis the number of unpaired electrons.
(hy The number of unpaired electrons in the complex points out the geometry
of the complex and vice versa. b pn
w,la
() During complex formation, Hund's rule of maximum multiplicity is strictly
followed. However, under the influence of strong ligands (like CN", OH,
etc.), the electrons may be forced to pair up against Hund's rule. However,
a weak ligand (like H,O) will not affect the electronic configuration of the
metal/metal ion.
will remain as such
When H,O is aligand
will change when
CN is a ligand
 Table 9.8: Geometry of Complexes on the Basis of Valence Bond Theor
ory
C.N. Hybridisation Bond Angle Geometry ples
2 Sp 180° Linear [Ag(NH,al. [Ag(CN)
3 sp2 120° Trigonal planar [Hgll
4
109°28 Tetrahedral Ni(CO) [ZnCl,1*. [Zn(NH) JB|
dsp? 90 Square planar [P(NH*. [Cu(CN),13
dsp or 120°, 90 Trigonal FelCO)s.MoC1.
sp'd bipyramidal CuCls
d'sp* or 90 Octahedral [FelCN)l. [Fe(CN)GI.
spd ICo(NH*.[PtCL*.
[Cr(NH)
(ii) Structures and Shapes of Complexes on the Basis of Valence Bond Thear
ory
a)Octahedral Complexes: The octahedral complexes are formed either by d'
or sp'd hybridisation and can be grouped into the following two categories
Inner Orbital Complexes: If the complex is formed by the use of inner d
orbitals, i.e., (n-1)d orbitals for hybridisation (written as d'sp), it is
called inner orbital complex. In the formation of inner orbital
complex, the electrons of the metal are forced to pair up and hence, the
complex will be either diamagnetic or will have lesser number of
unpaired electrons. Such a complex is also called low spin complex.
For example, [Fe(CN)1, [Cr(NH)s]**, [Co(NH)*, [Pt(NH)".
[Co(CN)°[Fe(CN)sl,etc.
Outer Orbital Complexes: If the complex is formed by the use of outer d
orbitals, i.e., nd orbitals for hybridisation (written as sp'd"), it is called
outer orbital complex. The outer orbital complexes have larger
number of unpaired electrons since the configuration of the metal 10n
remains undisturbed. Such a complex is also called high spin
comple.
For example, [Fe(H,0)%l", [C-(H,O)l*, 1Zn(NH).1*. ICoF,e
Examples of Inner Orbital Complexes with Coordination Number 6
ICr(NHe" complex ion [Hexaamminechromium(II1) ion]
Electronic configuration of Cr (Z 24) :=
[Ar]3d 4s*.
Oxidation state of chromium in the complex +3. =

Electronic configuration of Cr3*

[Ar]3d*.
=

Cr ion is formed by the loss of one 4s and two of the 3d elec rons.
The two 3d, one 4s and three d'sp
4p orbitals hybridise to B nlecule
hybrid orbitals. Six pairs of
electrons one from each NH3
igand), (shown by 1) occupy the six vacant hybrid orbitals.
Cr atom
3d 4s 4p
Cr" ion
d'sp hybridisation
dsp hybrid orbitals of Cr" ion 1 1 I
Vacant dsp*
hybrid orbitals

dsp hybrid orbitals in from

Six pairs of electrons
[Cr(NH) six NH3 ligands

NH3
HN NH

NH3
method
Fig.9.10: Formation of [Cr(NH)s complex ion by valence bond

Characteristics
state.
1. Complex ion has Cr°" in d'sp* hybridised
2. Innerd complex as inner d part in hybridisation.
orbitals take
moment of v15 B.M.
3. Highly paramagnetic with magnetic electrons.
lesser number of unpaired
4. Low spin complex a s it has
5. Octahedral geometry.
6. Bond angle = 90. orbital
Other examples of chromium complexes
with similar inner
structures a r e [Cr(CN)1and [Cr(H,O)1°".
[Hexaamminecobalt(11I) ion]
[Co(NH)" complex ion
of Co (Z= 27) o[Ar]3d 4s
Electronicconfiguration +3.
Oxidation state of cobalt in the complex=
configuration of Co" [Ar]3d5.
=

Electronic

Co atom 3d 4P

Co ion influence U NOI

Co ion under the
of strong NH3 ligands dsp hybridisation

dsp hybrid orbitals of Vacant dsp

Co ion hybrid orbitals

1 1 1 1Six pairs 1 T
1 of1 electrons
d'sp* hybrid orbitals in from
[Co(NH)6]* six NH ligands
3+
NH3
HN NH

NH
NH3
method
complex ion by valence bond
Fig.9.11: Formation of [Co(NH3)e1
 Characteristics

1. Complex ion has

Co*" in d'sp° hybridised state
2. Innerd complex as inner d orbitals take part in hybridi

it contains no unpaired tion

3. Diamagnetic since ectrons and its
moment is 0 (zero spin complex).
magnetic
4. Low spin complex as it contains paired electrons.
5. Octahedral geometry.
6. Bond angle
= 90°.
Other examples of cobalt complexes with similar inner ou.

structures are [Co(ox)al°, [Co(CN); and [Co(NO,)13 bital

orbital
FCNl complex ion [Hexacyanidoferrate(ll) ion]
Electronic configuration of Fe(Z= 26):[Ar]3d 42
Oxidation state of Fe in the complex =
+2.
Electronic configuration of Fe* = [Ar]3d".

Fe atom
3d 4s 4p
Fe ion
Fe ion under the influence 1u IT OON
of strong CN ligands
dsp hybridisation

dsp hybrid orbitals of Fe ion

Vacant d'sp
hybrid orbitals

d'sp hybrid orbitals in 1 1 1 1|1 |1 |1 1|

Fe(CN Six pairs of electrons from
six CN ligands
CN
C

CN N
CN
Fig.9.12: Formation of [Fe(CN)a1 complex ion by valence bond metnoo

Characteristics
1.
Complex ion has Fe in the d'sp3 hybridised state.
4Lnnerd complex as inner d orbitals take part in hybridisau
3.
Diamagnetic
is 0 (zero
since no unpaired electrons and magnetic
e t i c moment

spin complex).
4. Low
spin complex since it contains
5. Octahedral geometry. paired
electrons.
6. Bond
angle 90°.
=
 (Fe(CN)complex ion [Hexacyanidoferrate(III) ion]
Electronic configuration of Fe(Z 26): [Ar]
3d 4s.
=

Oxidation stateof Fe in the

complex = +3.
Electronic configuration of Fe3* [Ar]3d. =

Fe atom
3d 4s 4p
Fes ion 1 1 1 1 DO
Fe ion under the influence u |TL|1 DL
of strong CN ligands
dsp hybridisation
dsp* hybrid orbitals of
Fe ion Vacant d'sp
hybrid orbitals

dsp* hybrid orbitals in

Six pairs of electrons from
Fe(CN six CN ligands

3-
CN
CN CN

CN
CN
method
Fig.9.13: Formation of[Fe(CN). complex ion by valence bond

Characteristics
state.
1. Complex ion has Fe" in d'sp° hybridised
inner d orbitals take part in hybridisation.
2. Inner d complex as
of an unpaired electron.
3. Paramagnetic due to the presence
contains a n unpaired electron.
4. Low 8pin complex as it
5. Octahedral geometry.
6. Bond angle 90°.
=

Coordination Number 6
Examples of Outer Orbital Complexes with
[Hexafluoridocobaltate(11I) ion]
[CoFcomplex ion
configuration
Electronic Co (Z= 27): Ar]3d'4s3.
of
in the complex = +3.
Oxidation state of cobalt
Electronic configuration
of Co** =
[Ar}3d*.

Co atom 3d 4S 4p 4d

CoCoion
sp'd hybridisation
 sp°d hybrid orbitals
Vacant sp
of Co ion hybrid orbitals

sp'd hybrid orbitals 1|t|t||1u11|TU ITL Iti T]

Six pairs of electrons
in [CoF;l°" from six F ligands

Formation of [CoFlcomplex ion by valence bond method

Fig. 9.14:

Characteristics
state.
1. Complex ion has Co" in sp°d* hybridised
2. Outerd complex, F being a weak igand is unable to pair up electrons
of Co against Hund's rule. Therefore, outer d orbitals are used up for

taking electrons from F ion.

3. Paramagnetic due to presence of unpaired electrons and its magnetic

moment is v24 B.M.

4. High spin complex with four unpaired electrons.
5. Octahedral geometry.
6. Bond angle = 900°.

FelH,O* complex ion [Hexaaquairon(II) ion]

Electronic configuration of Fe (Z= 26): [Ar] 3d4s.
Oxidation state of Fe in the complex = +3.

Electronic configuration of Fe*" = [Ar]3d°.

Fe atom
3d 4s 4p 4d

Fe ion
sp'd hybridisation
spd hybrid orbitals IIRIT OO I
of Fe ion Vacant sp'd
hybrid orbitals
spd hybrid orbitals
in [FelH,O)** Six pairs of electrons
from six H20 ligands
HO
HOR

Fig. 9.15: Formation of [Fe(H,O) complex ion by valence bond metnoo

 Characteristics
1. Complex ion has Fes* in spd hybridised state.
2. Outer d complex, H,0 being a weak ligand does not affect the electronic

configuration of Fe*. Therefore, outer d orbitals will be used for taking

electron pairs from H20.
3. Highly Paramagnetic and its magnetic moment is v35 B.M.
4. High spin compler with five unpaired electrons.
5. Octahedral geometry.
6. Bond angle =90°.
(6) Tetrahedral Complexes: The tetrahedral complexes are formed by sp' hybridisation.
A few examples of such complexes are [Ni(NH3*, Ni(CO), [Zn(NH),J*"
[NiCl1.[MnCl,l. [CuCi,,etc.
Examples of Tetrahedral Complexes with Coordination Number 4

.Ni(NH complex ion [Tetraamminenickel{I) ion]

Electronic configuration of Ni (Z= 28): Ar] 3d°4s.
Oxidation state of Ni in the complex = +2.

Electronic configuration of Ni* = [Arj3d#

Ni atom
3d 4s 4p

Ni ion
sp' hybridisation
sp hybrid orbitals of TUITu ITIT M
Vacant sp
Niion hybrid orbitals

sp hybrid orbitals in 1 TU 1
Four pairs of
Ni(NH* electrons from
four NH ligands
2+

NH3

HN NH

NH3
ion by valence bond method
Formation of [Ni(NH,)4l" complex
Fig. 9.16:

Characteristics state.
contains Ni*" in sp° hybridised
1. Complex ion of unpaired electrons.
due to the presence
2. Paramagnetic
3. Tetrahedral geometry.
109°28'.
4. Bond angle
=
 Ni(CO), (Tetracarbonylnickel)
2 Electronic configuration of Ni (Z= 28):[Ar] 3d*4s2.
Oxidation state of Ni in the complex 0.
=

Ni atom 3d 4s
4p
N i atom after rearrange-
ment in the presence of
strong CO ligands
sp hybridisation

sp° hybrid orbitals of Ni

Vacant sp
hybrid orbitals
sp* hybrid orbitals in
[Ni(CO),12* Four pairs of electrons
from four cO ligands
CO
.
-.
Ni

OC CO

Co
Fig. 9.17: Formation of Ni(CO), complex ion by valence bond method

Characteristics
1. Complex has Ni in sp* hybridised state.
2. Diamagnetic due to the presence of paired electrons.
3. Tetrahedral geometry.
4. Bond angle = 109°28'.

(c)Square Planar Complexes: Square planar complexes are formed b y

hybridisation. Some examples of square planar complexes are NIC
Cu(NH)J". [Cu(CN),P, Pt(NH)J. [PtCil, etc.
Examples of Square Planar Complexes with Coordination Number 4

NiCN)Jcomplex ion [Tetracyanidonickelate(lI)ion]

Electronic configuration of Ni(Z 28) : [Ar] 3d°4s*.
Oxidation state of Ni in the complex +2. =

Electronic configuration of Ni2* =[Ar] 3d*.

Ni atom
3d 4s 4p

Ni2 ion TT
Ni under the influence
of strong CN
ligands dsp hybridisation
 dsp hybrid orbitals of
Ni ion Vacant dsp
hybrid orbitals
dsp hybrid orbitals in
[Ni(CN),12 Four pairs of electrons
from four CN ligandsS

CN CN

CN CN
Fig. 9.18: Formation of[Ni(CN). complex ion by valence bond method
Characteristics
1. The complex ion has Ni" in dsp* hybridised state.
2. Diamagnetic due to the presence of unpaired electrons.
3. Square planar geometry.
4. Bond angle = 90°.

.[Cu(CN)J complex ion [Tetracyanidocuprate(I) ion]

Electronic configuration of Cu(Z = 29) : [Ar] 3d"4s.
Oxidation state of Cu in the complex +2. =

Electronic configuration of Cu3" = [Ar] 3d.

Cu atom
3d 4s 4p

Cu ion I
Promotion of an unpaired
3d electron to a 4p orbital dsp hybridisation

dsp hybrid orbitals of Vacant dsp

Cu2 ion hybrid orbitals

in
dsp hybrid orbitals Four pairs of electrons
[CuCN) from four CN ligands

CN N

CN CN
complex ion by valk nce bond method
Fig.9.19: Formation of[Cu(CN),
Characteristics

ion has Cus" in hybridised state

dsp
1. The complex
due to the presence of one unpaired electron
2. Paramagnetic
geometry.
3. Square planar
= 90.
4. Bond angle