o.
en
cont having octahedal Complex changes to squau planah Comdes
then Unpaired e
-0 2-! 0-2 no chage.
Squane planan =) dsp.
4. Caystal ield thecy:
to this theONy, bond btun netal & digand is ionic (deto
Accei
Consldered as pt
pt hager in Cae ef -ve liard1(Fu
"Liqand1 av
"# Liqand neubal pt dipcles (o) dipoles.
towards metal.
The ve ot end neuta ligand pointing
metal the attractiue torces aise btun
If ligand apprach vepllive foxes arise ta
chaged digands. And cpluljive foces
metal ion and -vlsvely
ct metal
lp of e dqands le ot digad and d e
In tee metal , 5-d osbitals dyz sdzx day da-y,da) are degen exate.
cental meBal )
(Sphencally symmetical ield o ue charges surrad)
But in diqand,#e deereracy ef d obitals i6k dost,
preserxe
it esults in spling d-oxbitals into a sets wsth da enesyy
This process Is aled cystal ield splitting.
Maqitude @) catet c& spliting depends the 0.4 ard (Cny
and theit po[ition arourd the metal ion and stiength ot iqard).
The Qiting didhesent in difeunt stouctuwe, woith dilt GNe.
in Cclahekal: onplen :
|Caystal -eld liting centre
ente octahydYon Gong
In a octahedral Complex, metal Is at
and 6 coUerS ocCupied by Jigands.
|M
LKM’
In octahedval comp, the siqand approache
onhal atom along ais.
So 1epulsions btwn eg ovbitcli (pieent on aM).
diqjards gieaBer thane ta obital, 4digard,.
han tg nbit
So enerq ot eg olbital
obital i igher
hgher tan tgnidi. teg (datp, de)-deqeneyak
douaby
btun to 4ea 0tbital is (alled Cystal
The enevqy tb
tietd enegy. (CFSe) ctal held siahil esy!
YepteknBed by A (ov) 10 Ddrttiad
Dq. d quanta)
octahedal.
awg enerqy - o4Ao+a
dovbitals in
Spherical cnystal
d orbital o o eld (Hyrothetical)
metal ion.
The energY ct eq orbital iK 6Dq nigher tan hypothehial
erergy stale. tha oYbitals enegy Jowcr thàn hypothetica
energy stale.
are stabilived by -04 A6 and os bital1 Che de stabiled by
=)
eg 11) -0.4 X4tO662
tq
11
In df contiguvaten ,
F paising enecgy < cFse >> Strong igard. paiving taky pace r bg'eg'
Parning energy > CESE ak digand. airing doe,n't takes pne - ta
high spin comlex.
Joo spin CFSE O.4t35 high spin CFSE.
tag eg -0.4 Ao ta'eg
d² -0.8 A0
- .2Ao -1.20 o
tËeq? - Q Ao.
-l.4ho -|.2 Ao
d -1-8 A o -08 4U
d8
teq -|.2 Ao. -|.2 Ao
-0.6 Ao. - 0.6 Ao
Cnygtal ield plittng in terahedval comlen :
A equlay Hetrahedvon velated to a cube .Tre + iqands cing
altesna tive COTners ube . & metal is at cenve o he
Cube.
The ards pasies thiougn txe enthes .
In tena hedbal, Jigand appioache)
apploache) metal btun aNeJ . But the
divecion o sppoach
sppoach ot ligds doesnt coincdes exacts [Link] le,
The angqe btun eg onbitals cental metal ato LgAnd. is 544'
bton So t oibital cogey to
anqle
divection apprach ot dlgands than eg orbitals. So the energy o
tq moe than eg
bari certre.
alg-enexqy
d-ovbitals in
sphevical
d-ovbital
Free metal
-a.6x no. ef eq e + 0.4 Xno. thg e
For d' conquation,
into
3e aloays enters Oibital even
CPSE > -0.8 A+
Cystal ield plitting in saare planay :
In this Jigands appuoaches metal ion alonq
Ap
dz
dy dye den: de dy.
NOTE:
Ap: |.3 A.
Spectochemical erjer:
cvearing ol
Ligands can be ananged in a exies in the oider ot in
Strorg mostly sbog
stength. wec
CO> CN > NO, ’ 0- phen > di py > en >Py N N, >EbTA "'> NCS> H0
X- dunaY
> 0- donaY,
Ligand stength: C donaYS > N- donars
wak.
ong
Factors aecting Crngstal jied spliing'
p)
I. Geormetny stuctuve dh compex. n0.0f
a. Nabuse e Aigand 4 umber
3. onidation state e genbral metal ion Incveases
splitting incveDe
4. 1e a Metal same ono ct d'gands then calN
ield spltirg «a
[Link] de'
dB.
&. Notuve of cental mela! ion :(pindple q,no)
principle mo o A value.
3d< 4d< 58
34
as dectron dornty oocveou
3d td digand arpdhig beCGnAJ
eatie. vd brtore, soble
0. CfSE Value will be
Stuctwe ) octahedral.
Mn [AJadt: =)
t eq
J sthong liqand.
t eg'
-1.6A, +IPairing enexqy:
13
) tsat eg' t eg'
-2.4 A6 + 3P.
: Mn ion pairing energ Q8000 2 octahedval compk xes
spin k high spin complen & CPSe-.
PYiring energy < 40000 paivin energ > 2l00 (cese).
Jou9 spin. high spin.
CPSE = CFSE -0.6X Ao.
-6,6 x lo00
- 1.6x40000 + 28000.
-26o00 cm
-36000 Cm
Cclouy properties.
Substan ce absenb Jiqht c parttulr ANe dangth hen it ànn
as CoBour substance . The vemaining ,light ( waelengfhs) traniited.
foiide). the colot ot subs tang
veected. The tranj mi ted cclouy d dght is
Jight)h
(the compilevmientay colouY ct absorbed
waue dength ct abiekel Absorbed dight - transmi ed dight (ompleMentay
light (inm)
400- 435 uidlet yelkguw qree).
435 - 480 yelow.
blue Indigo
480 - 490 orange.
qreen-blu.
440- 500 Yed .
blue-qieen
purple.
500-560. qreen
uiolet
560- 580 yellaw qieen
580-595 . yellaw. blue /indigo
545- 605 fren-blu
Yed. blue-qreen.
605- 450 - )
Yellouw Draus backS o cnystalyjeld teoy
yellouwqnen
Orànge " H considers ony metal lon d-c
Red. blue qreen . 1his theony Unable to erplain atiyat
abt valative sbergth of igand,
H,0 > oH in soechochemcal seaie!
violek greon blue. g: why
Blue. " k didn't considey the covalent chanectr
Jigand oniC bond.
d metal diqand
H couldo't exçlaln #bonding cowyler.