ponding in coodination Compoundo.

c) Valence bond theoy (VBT)

cü) crystal Field (CFT)
(o) igand ield
theorg
theony (LFT)
(i) Molecular orbital theong MoT)

valene bond theoy

Correlates xpeimental
Linus pauling
magnetic moment with hy bidisation t complex
Each ligand Con touns a lone pir o electoas
Present in hy bñd (o orbital.
CMI Accommadates Vacant orbital5

accept lona paY from ligands.

me pair up electrons aoìnt
Bome
in order to Proide Vac ant
to Hun d'b rule

orbitals under the infl4ene of etreng

etc.
ligando like
Cental metal ion
Vacant or bitale
bidization be fore the Complex
underg o hy
and thase orbital formo
formation bonds by
Coordinoate covalent ove la pping
or bi tals of ligand.
flled
 The -orbi tol
involved in the hy bridization.
may be etts othor inner (n-)d or bital or
Outer nd - Or bitals Tho.
Lompleza. omed.
in these two

(n-)d or bj l nd orbital
invo lve involve
\ow spìn
spin omplex higr spin omplex
(on (o1)

inner spin complex Outer spin ompex

spin paired con
complex. spin tree eompler.
electron of certral metal o2.
Non

remain
bonaing un affected and do not tare part
chemica bonding
betweon te 1isand
GAen Areater the
overlapring
the hybi dised metal Orbita).
or bital and
greate is the bond etngto.

coordinotion Type af
hy bridisation.
ohape exAmple
numbea

9. |inear

Tigonal pannar
Spd Tetahedra)
4 dsp Sauae. panar
spd Tigonal bipyamdal
dsp square Pyramida)
octa he dra
d²sp> octahedral
Coordination number and shapes of complex
Coordin ation Geometrical shape Examp les of complex
Number Hybridise d orbital of the complex
[Ag(NH3)2]*
L -M
incar
[Ag(CN)2]

sp2 [Hgl,J
Trigonal planar
[FeC1,1
[Ni(CO),Jº (Zn(NH,)4]*2
109°28

4 sp3 (ZnC14]-2,
L [CuX}-2
where X = CN
Tetra hedral
CI, Br, I, CNS
L L
dsp2 90
! 90°X)90 [Ni(CN)4]-2
4
(n-1)d2-2 orbital]
L
90°

L [P(NH,),]:2
Square planar

5 sp³d M [Fe (C0);]

[nd,' orbital]

Trigonal bipyram idal

dsp'; 90°
5
[(n-)dx2y2 orbital] [CuCl,]
Lo
L
Square pyram idal
d'sp'
a) d²sp3 [Fe(CN ),]'.[Fe(CN ),J3
[d x y2 & d of (n-1)]
[Co(NH,)%]*3
90° M

6
spd2.
b)sp'd? [Mn(H,0),P*.[Fe(H,0),3*,
|nd,2,2
2-y2 &nd,] L [CoF,]. [Co(H,0 );12*,
Octahedral [Co(H,0)6l3", [FeF,P -
the no of. onpaied electon in the omplex.
points out tha 3eoetny of the. complez
ab well as hy bidí ba tion cartral metal
jon an d vice- versa.

In prattca ho of. npaired electrons.

in a comples found from
magnetíc mea Suremanto.

I the. Con tins Unpaied electron

complex
it i6 para magretic in nature

not contin Unpaired electos

diamagnetfc.
M.

n=0af. npaied electons.

basis
t complex
reomety dep ence opon
TFe shape of omplexe
control atom.
otate ot
hy bsdizatfon

octahadal complexes:
tuwo t7pe of hy bhdizaton

sp2.
Asp> outor orbital
oroital omplee complex.
irner
4 Co FJ
Gauare
planer omplex.
These formed due to dsp hybidiation,

Tetrahedral omplexe.
Thes e formed due
duue to sp hy bidisation

Nicj²
Aplicatip YeT
Ci) Low 9pin inner orbi l complex).
formed -) d ns, and nP rbtials hybsdiat
In Such complexes all o non

bondinq electonb of metal tom 9et

paired siving dia magnetc complex

with \ow magneic monent.

complex fomed the Se of inner

orbitals are diamagneic have
veduad Paramagnetis , These ae

called lou opin or

spin paied
Complexes.

spin outer or bi tal ) complexes.

cü) igh
and d Vacam orbita)
fomed y
A no furthar pairing of valere electron.
takec plaue. in fiel d of ligands.
Thase, 9enerally hdgh va he t ma gneti moment
 The Outer or btal
hih-spin Or Spin free.
(omplex hae greater bum ber of unpaired.
electos.

Eg
[nicl4J

Acial Cases

.
unpaird electron s
<eVen though NH
inner erbital Complex
strong field ligand
OccuYS
no
pairing p
becawe two d- orbitos are avi la ble for
hy bidiba tion.
6 NH act
M= oBM
co (NH)sd
feld ligand. form inner
etrong
orbital compl
.M 4.84 BM
e (ut)
Sill could
etng eld ligand but
electrono.
pair up the
expected to be tettahedal
uoith hybi diatin,
nt
tfe epen ment indicates that the
but
complez ib square planner rth dep
fails to
hybidsation .

pauling VBT

xplain the geonmety

 Ni 2+
tahadral omplex uo hether etrng
Reld we aK field re
paramagnehc orth
and outer or bital omplexes
2.+
like.

other coKcephione, are

[Ni FOJ-2.
SP2

Drawback · valence ond teory

invoves number of asum ptions.
not give auan titative inter pretation.
it does
magnetic data
oR
it does not explain tte colour exhibite by
oordination Compoundo.
it does no t make, exact pre dietions regardiy
the totta hedal and suare planar Structues.
of - 4- coos nate Lomplex
does not give uantitatve interpre tation.
the -tter mody rnamic or kinetic stabilties

of coordinaton Lompoundo.
It oes not distinguluh between weak

and strog 1igands.

 feld tkeory (cFT)
yotal
(CFr) i5
The cryotal eld theogConbidere the metal
electwstotíc model which
to be, ionic arising purely
-ligand bond the,
interaction between
Rro electosBatic.
meta) ion and tre ligand.
Ligands Ore tteate poit chorge,
in case o
Case
anions and dipoles
neutral molecul es.
Arangement af |lgonds the comtral
around

matal jon Such that tFe repulsì ons between

are ninimum.
and een tal metal Ton
ligande
specfic geomety to complex
It esults
takes place un der
d- orbtlo
spliting ot Ifgande called
Ssymetic infuene af
field eplitting af- d-orbi tals.
as erystal
loetween tia tw o
The erersy difference.
levels called crsstal
sets ot eneray
and i5 repreJented
fteld splittig enerey

-meuresthe cstal ield strenott.

of tre llgand.

be noted that tte crystal ield

OCCUYs \n Buch a way that the
averoge. eneray af the d o b i tls does.
not change.
 octahe dal
field optting io
num bo -b)
(omplex ( coordino tion
rr ounded 6 ligando
Cental metal ion ib
octa hadral geoatry.
the axib veulting
along
C+x-x, t9-9, +Z - )

to axial aRproach f ligands eig

Due

face. more epalsions.

orbi tals (dag. dz)
energy leve l onsequent .
and goqs to higher
oYbi tals goa to day dyz, dzz) lower.
teg
ener oy. level.

eero
orbital. eg orbita)
tag
2o

cyutal feld splitting enerey.

the thee Or bitals lie at an

Thio meanb that
that is (2/5) Ao be low tfe average
energy
d-orbital and the two d-orbitalb.
energy
above e aVeroe.
|ie at an enery dxyt dz2

ehery,

Averaoe. enersy
of orbltal n?
speri cal crzta)
das dyz dzx
d-orbia jn fre ion. ffeld:
 doO:4
Ao. -.4
(-o.4
tagb gand |iSt.
eg
tag sand ll
o)] o-b (2)+-o4
4do -0 =
spin (louw comple) spin (hign
paiing.
tag
tal orbi orbital eq enter
in
in enre electron
ctron 4th
d.
(P) Consideve also eneroYes
velue accUrate calcalate TO
FSE
no.a4 Y-
to. bior
Lag
alorbi n
o.bg)
Ao (-0.4
x+
octahedral
(CFSE) eneroy tion liza tnbi fied crystal
 CFSEfor

guration
Confi
different

‘ Distribution
Orbitalstg strongin
configurations
T
field
‘ ‘
orbitals
in
both
-1.8
-24Ao -1.6Ao -12An
-2.0 A unpaired
energysationStabili
0.8Ao0.4 An
electronst orbitals
0.0 -0.6 -1.2 weak

HN No. of
and
0 1 2 1 0 1 3 1
strongh
field

‘ Distribution
weak in

field

orbitals
‘-0.0 Ao
-0.6 -1.2 0.8
-0.4Ao -0.6Ao-1.2 A
-0.8Ao-0.4Ao
electrons Stabili
energysation

unpaired No. of
2 3 4 5 4 3 2 1
2. crystal feld gplting tetrahedral omploes.
The Rour ligande pproah the cont ral
metal atom the divection of the.
along
leading diogonals.
fold degenarate. Get ha.
than three Rold dogeneate
lower ener 7
set to
t'
9 ' i b not wed to
to denote
The subscópt
testra hedral tomplezes.
the tuo set in
in tetta hedral is Gmaller
Complexes is
A The
than that in Case, octahedral complexes.

nersy donoted in.

Crystal splitting
teta hedtal camplex (0t)

differene of eneroy repesente

do

ib not able to force tthe electron

This eeray euch tetraedval Lomplexa
to par p oPin can figuration
have high
 CFSE co. bx + o4y)st.
ho. af. e ln e. orbi l
no . ot e in t orbi ta)
y

oribta)
Factors datermining the magnitude af the
eneray (A)
splitting
). Nature af ligand.
ligand
depend upon the naure af
The A Vaue Ji sand.
4 The dapenda on the tandany
cantral matal ion.
interact wit the
to
ligand which cause
The
Small o Value large o value

Weak field lgond erong feld lisan d.

The li9onds Can be arranged in the.

shength spectrochemical
increcsing feld
bene.

<F <oH

< Heo < NCs < edta < nH

Cao4

L en
above,
seneral tFe llsan d ying
cre called field lgand and.
Hoo
Cawe greater crastal fie d splitin
thay
(oo high)
 On the other hand the li9ande water
and elow called weak freld llgand and
Caule. lewer crystal ffeld eptting (louw Ao)
oxidation State. of the metal ion.

Higher he jonic on the cental

harge
Oreater the value.o A
metal lon -the

(a)
more for o(Heo than

Go(H)j*
3ame no. af d electrons. and
a) caton havng
ame eometc cations witth igher
the
oxi dation state ha large Nalue af Ao.
2+

wirt the eame charges but th.

(c) cation
d- eleetrons the. magoitade
difter ent no

with increae t no: f.

of Do decveases
electrons. 2+

V (de)
(347)
() Nature af the metal ion.

The for milar compleza in tte

Bame oxi dation State. ncreases by 3O -502.

gotng
< 4d Senes < 5dseries

A a Consequuence. al thib
coordination entitiea

f second and third transition senes have

low spin complexes

grea ter tonden to fom
sei es.
compored to the fint transition
al

3t
Bt

aeomety o4 the complex.

Ao

At = Do (o.45 D)

((-33 A)

CFT
APplication
and low Sp)n comple e.
1. igh spin
Due
ChMI
tettahedral in
* Ligands approach
mibe. epuleions among thamse lves.
ini mi6e
Order to mini
approach tag orbi au face.
pue to
vepulbions then 2g orbials
more
 ib le -thon the eneroy vegkised for
Complex ill be high spin.
electron pairing the.
Complex (do<P)
enersy veguived for.
o ib greater than
greater
I¬
wìl be low sn
electron Painng the complez
Complez (Ao> P)
do (um) P(oa)
I7b00
law spin.

17600 igh spo.

st. teld 1lsand foroo - Lous spin.

spn.
weaK ield (igands fon- high
are a\ways low.
4d and complexes
ireapective ot strength of
spin (0o large)
the llgond.
enti Hes more
to d7 coordinaton
as compared o wak
btable for strong fed
feld
High and low spin
OccUY
ony tor
d metel comple.
colour in coor dinaton compoun ds.
(

field theory odti butes the

* The crystal
colour of the Coordi nation Campo un ds to
d-d transition of the electron.
 ib ipor tant to note that in the absence, f
oplitting doe not
ligand cyatal field splitting OCCUY

and honce. the Bubstance. ie colour less,

haneitn Cannot OccuY.

ha one. uppaie d electron.

which Ghows transtion a

abrb yellow green

vìolet colour .
appea

eolourles
heaty i5 colour less ut
Cuso
jb blue in colour.
CUso4.
Nicla i6
by
watex,
dsolved in
|igand ethan J,2
I4 the bidentade
diamine. (en) progreuivey odded cauing
colour changes.
2+

Pale blue
2

Bue/ pnple
violet

are

contiguathon and are olour lew due to

epn- torbfclden tyansition . even though
5 un paired eletron presen t dd taniso
not Oc Cr.
 for tree. complexes. of Ccoao)
o(t>) and
cnor gies.
crystal field oplitting

Wave numer.

3+

Small
inter mediate larse
Ao vale.
nterme diate. \arse.
exitaton Small
ener y
infernne ate 6mall
Adsorphiar. ) lar ge
usave lengt
Blue Violet
olour ahsorbed Orange

ye llou orang e yellow.

olour +ransmitted Blue.

Limitation af Crattal feld thecog

The aJumpion that ligand s are
point charges
that anionic I aande Should exer t
it followb
the greateot spliting effect
The anionic lisand aetually ate foond at the

low end of the spectrochemical Seies

does not take. into a Ccount the coNalent

Jt
charac ter of bondi ng between the igand
and CMI .
 In otrong feld o4 an octahedral

complex tho Value CFSE

con fi guration ib.

etrong feld
lisand
CFSE = ( o.42 + o.by)Ao.

=Fo4 (6) 4 o-bo] Ao.

tag hhh
CFSE =-2. 4 o

2. electronic con fieurartion of cunn)J2 2+

on the

basj CFT.

Btrong Aeld lsan t

tog
eg
teg

confisation of LFe(u)]
3 The lisand
CH strong fie ld

teg
(tog, eg°)