iatins

idatins G VBT;

No quantiHativa cxplanaton to pre dicd h

Outos o inno 0obital cpa.
available in Ves
yDees4 not bxplain the pre ferenca geomtiy

on the hatue o bigand, VBT annol

opkin he elabive Stabilib es for lipeunt geematvça
in C.
cp
No explanation is aviatl ior the chasactorit
colocu he cpx in Vo
No plaration yorlability 2 inesthass 9
motal px availabein Ve

kigk er leval.
Dn g it i 8aid dhat the gcemalrg 4 he
x can be prodicted yaom I5 magpebie mome nt t
is magbeic
when two possibihtes lead to sno
but
Lunpasted' , e taid magnetic aateyi
no Of
Cvitevicn pals to plain idontty he geomety.

bre

bot asp
Ohe Lcmpaie d eloctioh,
 Sane
eprerent in e ions au jonic
A cpx which ha lors
prasent in ye lons au covalent px, 13 ut Pome
ionie epr how covalnt Props high tolubliy
higk o lab ihy be) in Drg soh ert.

covalent chaacby
to be inerease with inc ceup in

D) ()
Covalen jonic Covalen

expe cta to be Zather yhaen tat with

Covalas
pr But in ie,nef any expoximen tally sypotod.

han T.
No oxplaration availabe yo ha spin
isomeviaro yund in mauy epx (eg: te cp) nonsla
* The spin ony magneit moment hot

always 2cccuate wrth. ep. values. he deialin

to otte yaetos, orb. condibution,
Spin- orb conpling , spin lme ism etty,s
x Relative Stabiliy Congeners'epx o
Reason bekind u non.- pxistence o may
NI
 motal ion
cpx is a combination

puounael by igaroly.
point changer etiner
huclos
atloction e ist betwOen
Force f
Meteljon - Ve Chage ths,ligand.
cueve meokil
The netal e maintain their

jdertity ionlgnd
y he only in to action botwcr metal
elocteostatie
coralent in teractien
* No consicorati'on of

botw eer matalALigandtio

FDIceOfydepuion exis, betwen DA
DY
hetal iorn Athat igaro
Repusive foxes cesporaible foo
two ses
spltting ef fie degeresate d o hitols in to
e, ariald (cloukly degeneabe) og A oabit als 4 non
anial (eriply degeresate) bg oykidalo
, duzd .
dayend

drey dy?
Cytal pialal plitting in Oh epx!
ehikonmont igaik
PPlo acking along he onis.

The or bitals
Lyingalong the onis a, eg
avia) oibijals (dy, ds) expevienc more
kepulsion fhan non ajal tag ovbitale (day, dya,
da2)
* Thus the o five dugenerate o obitali
Split ito two Sofs osbitals at
igha errgy han, Esg orbs.
The etent to wich
sepu ted in oh eni AOmant olenoteol by Ao

formation o cpx involves two- stop

) ligan ds appaDpeoack
t0aeh metal atom
abom,, peoducing
hupothetical phericalietel which seells
tepellk all of
he d-orbs o the fama
Same 2XEent,
On giek wich splih
 + 3/ ho = t0.6 0o
or 6 Dq

2/5
or 4 D9
d-brbs in
froe metal
d-obc io tg
liqand Crystal pield
jon field
spltting in
Oh enviH onment

) High spin epx

(spin frpe cpx)
Dh tho cas e f weak gicd ligandr

whese

p Paiaing erey
folocer hends Rule.
Filli ng p ef
Ha0, F, B,OH ebty

) Low spin cp
(spin paied epx )
fhe ease strorg

whose
 Flling ep of e against Hurb eula
sttong pield Ligandr CN, co, NH¡ No,
CFSE
Cystal field stabili ation onongy i dgined aa
Dnegy dli. bet. e, clee.ten'g in tho igand
yield Athe baryconkei.

6D +0.6Ao
6D

414

(Sng (boak 3

Field) field)
CFSE = (5 X-0.4) bo
CFSE - (8 x-04) +(a xo6))
-|-2.0|Ao
(-l,2 + L.2) do
the Value Ao in
staong yield ie kighas than
cjelal en
viRonm ent
sc
(aygtal tiel splitting in Td goemetyy
* Dn a geemctg envitonment tho igands
in botwcor the qxes.
2

M.

* Jhe orbital: ying be

be tiveen
tio tho

Cax) expo iences

hen axial E g. brbs (dy, dyz, cbx)
lepulelon 'han axial eg abs (dy,d )
+ Thus the fiva dogenesate d orbs split into
tuo sot witt orbs at highe than cnogy
osbs.

ohich ta
he Xtent to cwhich. obs
Aeparatao in To enviaonnont is lenotod by O
The g subacaiph cokich weso cwed for the
Oh ied te no longe garopriate Lacare the

The ciyrtal piols splitirg in TA i smale

becaue o.less
han that in Oh pielel
lgand1 thog a Gpr ae hot
Orb splitting enesgics ln
cagh fo fovce e tpais
age en
 or 4 D

Ener9y
d-orbs in bD
digand
tield
Cytalfiald
Spliting in
Td eniADnmeht

Cryetal ficld splhiting in sgp envikon mont

*Tp the two ktans anial igead
geometrg takon to inginlty hen the 89PP
cylal fietd iu lavelopacl.
* This tempval o/ igand yom 2 axis
lead do less opulion along 2 axis . fo the
orbitals having 2componerk (dya dyz ) will
have lowes onongy than
Than
? th the} orbs,
Tho
da2y?
argy
En
Ao dy
dy dz2
tag dxdyz
a2,dyz aqs
(a) (b)
Rer
hat
ie
bacomes
undugeing
totragonally
2- axis elongotion Auch
diitortod a) ana finally
eathas Limit (0

Dn sgp cpx,tho liganol 4ppoachirg

dey
kigbeit iopulsion
bi tal. So it expe sjonces ha
and get highey oneg
* The dg lobe wh'eh à inbatwecn he gard
will alo xpoience epuloion Cetabivoly Loss) bot!
and will get highe cnergy nen
rett to day.
* s these s ho Acpuleien along 2axis iE
ika clativoly lower in cnavgy.
* Tn sy, d , y orbs ,the presenca 2-c0mp
stabi izes the obs but he p esena of X Y comps lw
han that. lowest
dostatiiae hem, Anlso thay cwill be tn the
Dnorgy

Crystal piald spltbrg in sg Pyramidlal geom,

geomaby
ho ligon db
ypsoaching along dy l orbitak and
igand izaqoaching along os ob.
So + ds-y' o b oxpeviancas hugh sopulsion
and gee kighos enorsy.
 Pyami) (
(octaeda)
dyz dnË
-ba dy
Ao
Aner99
b
1)
M
geomeby
syP to
Ayand Cial
gaomel1y
ol
yom digard s)Remo
val
axial ore
way. dorivodin
two
can ramioal
a Py g inorbs dsplitirg
f The
oys dus, Dsbs
dx han tepulion bva
oxpevjcrees Chages.
more
bgand he erploane hein
dying orb dy
plared
 (oDa dxu'

LoD
duy

dy
dez
dus,dy2
daz,dyz
(squave
(Squar o. Pyramidal)
ai Planas )
bipyamidal
Crystal Fielel splitting e tha in Teigenal
epyikonment:
trigpral bipy ramialal geomabry

do o btial oxporie ncoe the moxinum, eepulsion by

the dinect
dinect appaoach igans

d d l y Dibitalk lying in
The'diy?
plaro do not icactly aco all the
9uatovial
but ae egualy eted anodo
e9uatial biyand
Gpulsionsome extont, than das 4
epevenccs dhe
pacing hu loart, aguleion
dyYeom the lyand.
 dz?

Energg.

(Trigonal
Bipruidlal)

Factors appocting ho crgstal ficld splitting

pauame tor:
The magniBude p rgrla pield plikting
depend eo badhbo both metal

ioo 'gand.istxo inihi

1a 2 Oxidation state! with ha Inciaase in

pori tiva caidation iate the spliting ihe
1Thcrcaoe in Oxdn tato jncroas es the
oxdn state oloctuosbatHe
melal--ligand attiaction. nd alio decxcases h
ionic kadica f thi metal contor,
Thase yaotors
oad t the inercast n the
pliting. maghitucl
kilo kaypse'
 fo m)id)2.9a 2o. 76

Pasition f matal contas in pevcd'e gep

inescascs
don in a gp. Egpo ctive Ne: chag0
acc umwation Lao seseening dep eloctaoru)
addiien to this theve s highe gpatial listibtion
the largor d. orbitals the hoavies congo na
which enhanes he ioteraction with dhe point - Lika
ig and chages.
Ihase two facfors ncscasoe tBo

3d yd sd
Coystal piold
plieting poue
>nd .sesies PrcI
Ist Eransihon series increasOs bg

hdt. Seies 3soje ) 30y,

) Do =22,90 kk
Do = 39. to

i) Excharg Highe the exehango ene 9y

dtability in orderto get
highas will be ha
4
abilised throug h axcharg energy
Natue of
epot ef liganda on tha plitting yi
3iren by Spoctochemical
spacttochenical seies.
n B < sCN c N a CMesOZ wua (0)4,
<Reo < ox,o2-ZH)o Nee- <Ne<edta

<p9

Spli Hing powcs / Dgand

Seies è, cons tauctedorm specltal
data meta cpxs.

The igan dls positienel at the ight end

called shong yiold igandi
cwich the
Caeses
incroase io cpltig.
Ihe ligarols peritierod ho
he gejes aue yiclslbgand lekich
called cveak

auses he lessspitting o the osbitals.

pplicatiors oy T!
CF Can
prodict tho clecbron staibutien
paten in the splittool orbitala . Flom tht
no. erpaite es can bo ealcu lated and
fhis
the spin only magretic moment can be
aom

Cand tal
mebal ion
¿lec. conf of Mn
M n tbon'lb
A] 3d5
Haos a cwegk
Lingand
 ds
9N Contain 5 wrpaiud

*. Di paramgrate

-V35
=5.9) BM,
caleulatod
O Motat. bigand bond enengy cn bo
SE I
theorctiza lMy by conideu ing the contribeutian
this calulatod value
enpeimental vaues.
Fos

he caleulatod energy Pos

matal Liyand bond
oidhout the
with pce tontibution ho r alue becomes
bet al

595 Ilnol whick nicoly g1 ce

Valeu 669 H/nol han that.
ordes ie,
O Th aplainig the natwal stabiiy
the cse plays an
hu Dring. willana stailiy
Import eol .

soias b called Ding- llams tability ndu

jor oh cpk
 One cfof fators for the
ha dhis

increare o cpse along along u

givas an additonal csce o Cu2 cpo
Th the calculation hyclation onongiag
matal ion he Consideraton epie plays a mayor
tole. T,, the contaibakinn o f re s Ubstsactod
Yeom the estimated value, i give the erpaximantal
hydiatien tnhaly
o
6Vaiaton
Aist t ansition seoies
A can be explaincd
explained by tBe considesation ey fre
OThe çco con taibution iis invo lued in the
cletes min ation te prof esved
In gen ceal
Steroo chemuty
oh
Of
han bat ef a geomctry Theu ip Oh.g isgoomatry
conertd
into a.g There Cuill be a -lass
This loss
cellool as oh sito, sclotion
D he oh energy OsSE)
steucture p ofeune arexgy (0s PE)