Crystalfieldtheory:anelectrostaticmodel

Themetalionwillbepositiveandthereforeattractthenegativelychargedligands

Butthereareelectronsinthemetalorbitals,whichwillexperiencerepulsions
withthenegativelychargedligands
 CrystalFieldTheory
Focus: energiesofthedorbitals

Assumptions
1. Ligands:negativepointcharges
2. Metalligandbonding: entirelyionic

strongfield(lowspin):largesplittingofdorbitals
weakfield(highspin):smallsplittingofd
orbitals
Ligand/dorbitalinteractions

Orbitalspointatligands
(maximumrepulsion)

Orbitalspoint
betweenligands
(lesspronouncedrepulsion)
Thetwoeffectsofthecrystalfield
Splittingofdorbitalsinanoctahedralfield

eg

3/5o

o
2/5o
t2g

oisthecrystalfieldsplitting

E(t2g)=0.4ox3=1.2o
E(eg)=+0.6ox2=+1.2o
 Themagnitudeofthesplitting
(ligandeffect)

Weak
Strong
field
field

Thespectrochemicalseries
CO,CN>phen>NO2>en>NH3>NCS>H2O>F>RCO2>OH>Cl>Br>I
 Themagnitudeofthesplitting
(metalioneffect)

Weak
Strong
field
field

increaseswithincreasingformalchargeonthemetalion
increasesongoingdowntheperiodictable
Thesplittingconstant
mustdependonboththe
ligandandthemetal.

o M nlLl x 103

Predictsvalueof(cm1)
nlis#ofligandsLl
 Placingelectronsindorbitals
StrongfieldWeakfield StrongfieldWeakfield
d1 d2

d3 d4
Whenthe4thelectronisassigneditwilleithergointothehigher
energyegorbitalatanenergycostof0orbepairedatanenergy
costof,thepairingenergy.

d4

Strongfield= Weakfield=
Lowspin Highspin
(2unpaired) (4unpaired)

< o > o
Notes:thepairingenergy,P,ismadeupoftwoparts.1)Coulombic
repulsionenergycausedbyhavingtwoelectronsinsameorbital
 PairingEnergy,
Thepairingenergy,,ismadeupoftwoparts.
1) Coulombicrepulsionenergycausedbyhavingtwoelectronsin
sameorbital.Destabilizingenergycontributionofcforeach
doublyoccupiedorbital.
2) Exchangestabilizingenergyforeachpairofelectronshavingthe
samespinandsameenergy.Stabilizingcontributionofefor
eachpairhavingsamespinandsameenergy

=sumofallcandeinteractions
 Placingelectronsindorbitals

d5 d6 d7

1u.e. 5u.e. 0u.e. 4u.e. 1u.e. 3u.e.

d8 d9 d10

2u.e. 2u.e. 1u.e. 1u.e. 0u.e. 0u.e.

Positive
favorshigh
spin.Neg
favorslow
spin.
EnthalpyofHydrationofhexahydrate
Splittingofdorbitalsinatetrahedralfield

t2

t=4/9o

Alwaysweakfield(highspin)
Magneticpropertiesofmetalcomplexes

Diamagneticcomplexes
verysmallrepulsive
interactionwithexternal
magneticfield
nounpairedelectrons

Paramagneticcomplexes
attractiveinteractionwith s n(n 2)
externalmagneticfield
someunpairedelectrons
Measuredmagneticmomentsincludecontributionsfromboth
spinandorbitalspin.Inthefirsttransitionseriescomplexesthe
orbitalcontributionissmallandusuallyignored.
 Octahedral,Tetrahedral&SquarePlanar
CFSplittingpatternforvarious
moleculargeometry
dx2y2 dz2
dx2y2
Tetrahedral Squareplanar
Octahedral
dxy dyz dxz dxy
M
M M

dz2

dx2y2 dz2 dxz dyz

dxy dyz dxz
Mostlyd
Mostlyd8
8
PairingenergyVs.
PairingenergyVs. SmallHighSpin
SmallHighSpin (MajorityLowspin)
(MajorityLowspin)
Weakfield<Pe
Weakfield<Pe Strongfieldligands
Strongfieldligands
Strongfield>Pe
Strongfield>Pe i.e.,Pd
i.e.,Pd2+,Pt
,Pt2+,Ir
,Ir+,Au
2+ 2+ + 3+
,Au3+
 Summary
Crystal Field Theory provides a basis for explaining many
features of transitionmetal complexes. Examples include why
transitionmetalcomplexesarehighlycolored,andwhysomeare
paramagneticwhileothersarediamagnetic.Thespectrochemical
series for ligands explains nicely the origin of color and
magnetism for these compounds. There is evidence to suggest
thatthemetalligandbondhascovalentcharacterwhichexplains
whythesecomplexesareverystable.MolecularOrbitalTheory
can also be used to describe the bonding scheme in these
complexes.Amoreindepthanalysisisrequiredhowever.
 Coordination Chemistry:
Molecular orbitals for metal complexes
LigandFieldTheory
Crystalfieldtheoryprovidesasimpleconceptual
modeland
canbeusedtointerpretspectraandthermochemicaldata
byappealingtoempiricalvaluesofo.Oncloser
inspection,
however,theCFTisdefectivebecauseittreatsligands
aspointchargesordipolesanddoesnottakeinto
account
theoverlapofligandandmetalorbitals.
Ligandfieldtheory,whichisanapplicationofmolecular
orbitaltheorythatconcentratesonthedorbitalsof
thecentral
metalatom,providesamoresubstantialframework
understan
dingo.Thevalenceorbitalsonthemetalandligandareused
MetalorbitalSymmetrylabelDegeneracy

sa1g1
px,py,pzt1u3
dxy,dyz,dzxt2g3
dx2y2,dz2eg2

Ligandcombinations
a1g:1+2+3+4+5+6
t1u:13,24,56
eg:12+34,26+251234

Thesesixcombinationsaccountsforalltheligandorbitals
ofsymmetry:Thereisnocombinationofligandsorbi
talsthathasthesymmetryofthemetalt2gorbitals,sothe
latterdonotparticipateinbonding.
Molecularorbitalsenergylevelsofatypicaloctahedral
complex
Sixbondingmolecularorbitalsofthecomplexaremainly
ligandorbitalincharacterinthesensethatc 2L>c2M.These
sixbondingorbitalscanaccommodatethe12electronsprovi
dedbythesixligandlonepairs.
Thenumbersofelectronstoaccommodateinadditiontothose
suppliedbytheligandsdependsonthenumberofdelectrons,
n,suppliedbythemetalatomorion.Thefrontierorbitalsof
thecomplexarethenonbondingentirelymetalt 2gorbitals
andtheantibondingegorbitals.Theoctahedralligandfield
splittingparameter,o,inthisapproachistheHOMOLUMO
separation(HighOccupationMolecularOrbitalLowUnoccu
pationMolecularOrbital).
InLFT,Themolecularorbitalsinvolvedarelargely,butnot
completely,confinedtothemetalatom.CFTexaggeratesthat
confinementbysupposingthatthedelectronsarestrictly
confinedtothemetal.
ThequalitativeMOTpermitsustoidentifymoredeeplythe
originandmagnitudeofthesplittingoftheorbitals .
d0-d10 electrons anti bonding
metal character

non bonding

6 ligands x 2e each

12 bonding e
ligand character
 Introducing -bonding

2 orbitals of -symmetry
on each ligand
We can build 12 group orbitals
of -symmetry
Bonding
Iftheligandsinacomplexhaveorbitalswithlocal
symmetry
withrespecttotheMLaxis(astwooftheporbitalsof
ahalide
ligandhave),theymayformbondingandantibondingmole
cularorbitalswiththemetalorbitals.Thecombination
havenet
overlapwiththemetalt2gorbitals,whicharetherefore
nolonger
purelynonbondingonthemetalatom.Dependingonrelative
ENergiesoftheligandandmetalorbitals,theenergies
ofthet2g
MOslieaboveorbelowtheenergiestheyhadasnonbonding
AO,sotheHOMOLUMOgap(thatis,o)isdecreseor
increase,
donorligandisaligandthat,beforeanybondingis
conside
red,hasfilledorbitalsofsymmetryaroundtheMLaxis.
Theenergiesofthesefullorbitalsareusually
closeto,but
somewhatlowerthan,thoseofthemetaldorbitals.We
need
consideronlythefullorbitalswhenconsideringthe
effects
ofbondinginthecomplex.SuchligandsincludeCl,Br
andH2O.Theneteffectisthatnonbondingmetaliont2g
orbitalsbecomeantibondingandhenceareraisedcloser
inenergytothemainlymetalantibondingegorbital.
Itfollowsthatstrongdonorligandsdecreaseo.

Theoverlapthatmayoccurbetweenaligandporbital
perpendiculartotheMLaxisandametaldxy
a) OverlapMetalt2g+orbitalb)OverlapMetalt2g+Metalt2g
c)OverlapMetalt2g+*orbital
Theeffectofbonding
ontheligandfield
splittingparameter.
Ligandsthatactas
donorsdecreaseo.

ML
Aacceptorligandisaligandthathasfilledorbitalsatlower
energiesthanmetalt2gorbitals,italsohasemptyorbitalsthat
areavailableforoccupation.Theacceptororbitalsarevacant
antibondingorbitalsontheligand,asinCOandN2,andthese
orbitalslieabovethemetaldorbitalsinenergy.Thedonor
characterofCOisverylowandinmostdmetalcarbonylcomp
lexesCOisanetacceptor.
Becausetheacceptororbitalsonmostligandsarehigherenergy
thanthemetaldorbitals.TheyformMOorbitalsinwhichthe
bondingt2gcombinationsarelargelyofmetaldorbitalscharacter.
Thenetresultisthatoisincreasedbytheacceptorinteraction.
Ligandsthatactas
acceptorsincreseso

ML
Theoverallorderofthespectrochemicalseriesmaybeinter
pretedinbroadtermsasdominatedbyeffect,andin
generaltheseriescanbeinterpretedasfollows:

increasingo
donor<weakdonor<noeffects<acceptor

Representativeligandsthatmatchtheseclassesare

I<Br<Cl<F<H2O<NH3<PR3<CO
donor<weakdonor<noeffects<acceptor

donorligandsdecreaseoandacceptorligands
increseo;thespectrochemicalseriesislargelya
consequenceoftheeffectsofbondingwhensuch
bondingisfeasible.
 Anti-bonding LUMO()

The CN- ligand

Someschematicdiagramsshowinghowpbondingoccurs
withaligandhavingadorbital(P),a*orbital,anda
vacantporbital.
ML6 -only bonding

d0-d10 electrons anti bonding

metal character

non bonding

6 ligands x 2e each
The bonding orbitals, essentially the ligand lone pairs,
12 bondingwill
e not be worked with further.
ligand character
 -bonding may be introduced
as a perturbation of the t2g/eg set:
Case 1 (CN-, CO, C2H4) t2g (*)
empty -orbitals on the ligands
ML -bonding (-back bonding)

t2g

eg
eg

o
o o has increased

t2g
Stabilization
t2g ()

ML6 ML6
(empty -orbitals on ligands)
-only +
 -bonding may be introduced
as a perturbation of the t2g/eg set.
Case 2 (Cl-, F-)
filled -orbitals on the ligands
LM -bonding
eg eg
o
t2g (*)
o has decreased
o

Destabilization

t2g

t2g
Stabilization
t2g ()

ML6 ML6
(filled -orbitals)
-only +
 Puttingitallonone
diagram.

Strong field / low spin Weak field / high spin

 SpectrochemicalSeries
Purelyligands:
en>NH3(orderofprotonbasicity)
donatingwhichdecreasessplittingandcauseshighspin:
:H2O>F>RCO2>OH>Cl>Br>I(alsoprotonbasicity)

Addinginwater,hydroxideandcarboxylate
:H2O>F>RCO2>OH>Cl>Br>I

acceptingligandsincreasesplittingandmaybelowspin
:CO,CN,>phenanthroline>NO2>NCS
 Mergingtogetspectrochemicalseries

CO,CN>phen>en>NH3>NCS>H2O>F>RCO2>OH>Cl>Br>I

Weakfield,
Strongfield, only donors
acceptors
small
large
highspin
lowspin
TurningtoSquarePlanarComplexes

Mostconvenienttousealocalcoordinate
z y
systemoneachligandwith
x

ypointingintowardsthemetal.pytobeused
forbonding.
zbeingperpendiculartothemolecularplane.pz
tobeusedforbondingperpendiculartothe
plane,.
xlyinginthemolecularplane.pxtobeused
forbondinginthemolecularplane,|.
 ML4 square planar complexes
ligand group orbitals and matching metal orbitals
 ML4 square planar complexes
MO diagram

-only bonding - bonding

 A crystal-field aproach: from octahedral to tetrahedral

L
L L L L
M M
L L L L
L

Less repulsions along the axes

where ligands are missing
A crystal-field aproach: from octahedral to tetrahedral

A correction to preserve
center of gravity
 The Jahn-Teller effect

Jahn-Teller theorem:
there cannot be unequal occupation of orbitals with identical energy

Molecules will distort to eliminate the degeneracy