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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
d8 d9 d10
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
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()
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.
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
L
L L L L
M M
L L L L
L
A correction to preserve
center of gravity
The Jahn-Teller effect
Jahn-Teller theorem:
there cannot be unequal occupation of orbitals with identical energy