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. IntensityofColor
Howintensityofcolorisexpressed
Aselectionruleisaquantummechanicalrulethatdescribesthetypesofquantum
mechanicaltransitionsthatarepermitted.
Theyreflecttherestrictionsimposedonthestatechangesforanatomormoleculeduring
anelectronictransition.
Transitionsnotpermittedbyselectionrulesaresaidforbidden,whichmeansthat
theoreticallytheymustnotoccur(butinpracticemayoccurwithverylowprobabilities).
1.Laporte SelectionRule
Statement: Onlyallowedtransitionsarethoseoccurringwitha
changeinparity(flipinthesignof one spatial coordinate.)OR
Duringanelectronictransitiontheazimuthal quantumnumbercan
changeonlyby 1( l =1)
TheLaporte selectionrulereflectsthefactthatforlighttointeract OttoLaporte
withamoleculeandbeabsorbed,thereshouldbeachangeindipole GermanAmericanPhysicist
moment.
Practical meaning of the Laporte rule
Gerade =symmetricwrt
Allowedtransitionsarethosewhichoccur
centreofinversion
betweengerade toungerade orungerade to
Ungerade =antisymmetric
gerade orbitals
wrtcentreofinversion
Allowed
gu&ug ThisruleaffectsOctahedraland
Squareplanarcomplexesasthey
Notallowed(FORBIDDEN) havecenterofsymmetry.
gg &uu
Tetrahedralcomplexesdonothave
t2g eg isforbiddenOR
centerofsymmetry:thereforethis
AccordingtoLaporte selectionrule
ruledoesnotapply
dd transitionsarenotallowed!
2.SpinSelectionRule
Statement :Thisrulestatesthattransitionsthatinvolveachangeinspin
multiplicityareforbidden.Accordingtothisrule,anytransitionforwhich
S =0isallowedand S 0isforbidden
d5Highspin(e.g [Mn(H2O)6]2+
eg eg
S =0 S 0 S 0Forbidden
Allowed Forbidden
Whydoweseeforbiddentransitionsatall?
Relaxationoftheselectionrules
Therearethreemechanismsthatallowforbidden
electronictransitionstobecomesomewhatallowed
resultinginsomeintensityofthecolorexpected.
1) Vibronic Coupling:Duringsomeunsymmetrical
vibrationsofamoleculetherecanbea
temporary/transientlossofthecentreofsymmetry.
Lossofcenterofsymmetryhelpstoovercomethe
Laporte selectionrule.Alsotimerequiredforan
electronictransitiontooccur(lifetime1018 sec)is
muchlessthanthetimerequiredforavibrationto
occur(lifetime1013 sec
2) Mixingofstates:Thestatesinacomplexarenever
pure,andsosomeofthesymmetryproperties(gor
u)ofneighboringstatesbecomemixedintothoseof
thestatesinvolvedinaforbiddentransition. For
examplemixingofd(gerade)andp(ungerade)
orbitals resultsinpartialbreakdownoftheLaporte
rule
3) Spinorbitcoupling:Partialliftingofthespinselection
rule ispossiblewhenthereiscouplingofthespinand
orbitalangularmomentum,knownasthespinorbit
coupling(commoninheaviertransitionmetals)
[Mn(H2O)6]2+
Thespectraofcomplexesoftetrahedralmetalions:
Aswehaveseen,atetrahedronhasno
centerofsymmetry,andsoorbitals insuch
symmetrycannotbegerade.Hencethed
levelsinatetrahedralcomplexaree andt2,
withnogforgerade.
ThislargelyovercomestheLaporte selection
rules,sothattetrahedralcomplexestendto
bemoreintenseincolor.Thus,weseethat
dissolvingCoCl2 inwaterproducesapale
pinksolutionof[Co(H2O)6]2+,butonadding
HCl tetrahedral[CoCl4]2 forms,whichhasa
veryintensebluecolor.
CobaltbluewasknowninChinabefore1400BCwhenitwasused
forpotteryglazes,butitwasalwaysararepigmentbecausecobalt
mineralswerescarce.Today,cobaltisstillusedtocolourporcelain,
pottery,glass,tilesandenameljewellery.Itsrichbluecolourisalso
knownasSvres blueandThnard blue
Thespectraofoctahedral[Co(H2O)6]2+ andtetrahedral[CoCl4]2 ions:
[CoCl4]2 Intenseddbandsintheblue
tetrahedralcomplex[CoCl4]2,as
comparedwiththemuchweaker
bandinthepinkoctahedralcomplex
[Co(H2O)6]2+.This differencearises
becausetheTd complexhasnocenter
ofsymmetry,helpingto
overcomethegg Laporte selection
rule.
[Co(H2O)6]2+
Classification of intensities of electronic transitions
Spinforbidden,
Laporte forbidden
(partly allowedbyspinorbit [Mn(H2O)6]2+ 0.1
coupling)
Spinallowed(octahedral
complex),
Laporte forbidden [Co(H2O)6]2+ 1 10
(partly allowedbyvibronic
couplinganddpmixing)
Spinallowed(tetrahedral
complex),
[CoCl4]2 50 150
Laporte allowed(butstillretain
someoriginalcharacter)
Spinallowed,
Laporte allowed KMnO4 1000 106
e.g.chargetransferbands
Molecularorbitalpicturerequiredtoexplainchargetransferspectra
Includesboth and (backbonding)bonding
t1u
Cr(CO)6
Mo(CO)6Colorless
W(CO)6
Howeversomecomplexesalsoshowaphenomenon
knownasFluorescence
Fluorescenceistheemissionoflightbyasubstancethat
hasabsorbedlightorotherelectromagneticradiation.In
mostcasestheemittedlighthasalongerwavelengthanda
lowerenergythantheabsorbedradiation.
SoifsuchcomplexesareirradiatedwithUVlight,the
excitedelectronwilllosesomeenergyandthenfallbackto
groundstateemitting(fluorescent)lightinthevisiblerange
Emissionspectra,Blacklight,UVAradiationandfluorescence
Quinine
Zn2SiO4
AdvantagesandDisadvantagesofCrystalFieldTheory
AdvantagesoverValenceBondtheory
1. Explainscolorsofcomplexes
2. Explainsmagneticpropertiesofcomplexes(withoutknowing
hybridization)andtemperaturedependenceofmagnetic
moments.
3. Classifiesligands asweakandstrong
4. Explainsanomaliesinphysicalpropertiesofmetalcomplexes
5. Explainsdistortioninshapeobservedforsomemetalcomplexes
Disadvantagesordrawbacks
1. Evidencesforthepresenceofcovalentbonding(orbitaloverlap)in
metalcomplexeshavebeendisregarded.
e.g DoesnotexplainwhyCOalthoughneutralisaverystrongligand
2. Cannotpredictshapeofcomplexes(sincenotbasedonhybridization)
3. ChargeTransferspectranotexplainedbyCFTalone
ProblemSolving
Anareawhichbridgesorganicandinorganicchemistry
Abranchofcoordinationchemistrywherethecomplexhasoneor
more metalcarbonbonds
Themetalligandinteractionsaremostly acidtype
MCbondcanbea typeor typebond
C C
M M *
C C
H3C
H2
C CH2
Pb
H3C
H2C CH
3
H2 C
CH3
Whatallcompoundsareconsideredasorganometallic?
CalwaysmoreelectronegativecomparedtoM
Theleadingjournalsofthefielddefinean"organometallic"compoundas
oneinwhichthereisabondinginteraction(ionicorcovalent,localizedor
delocalized)betweenoneormorecarbonatomsofanorganicgroupor
moleculeandamaingroup,transition,lanthanide,oractinidemetalatom
(oratoms).
Followinglongstandingtradition,organicderivativesofthemetalloids
suchasboron,silicon,germanium,arsenic,andtellurium alsoare
includedinthisdefinition.
Itisalsounderstoodthattheelementtowhichcarbonisboundismore
electropositivethancarbon inorganometallic chemistry.
Traditionalchemistsdonotagreeforclassifyingmetalcyanidecomplexes as
organometallic
ZeisesSalt Thefirsttransitionmetalorganometalliccompound
K2PtCl4 + C2H5OH
Discovery1827
WCZeise,Danish Structure~150years
pharmacist,I789 I847 later
The breakthrough, the isolation of a pure, crystalline compound came when Zeise added
Alsofatherofthe potassium chloride to a concentrated PtCl4 /ethyl alcohol reaction solution and
chemistryof evaporated the resulting solution. Beautiful lemon yellow crystals, often one half inch or
mercaptansRSH more in length were isolated. On longer exposure to air and light, they gradually became
covered with a black crust. They contained water of hydration, which was lost when they
were kept over concentrated sulfuric acid in vacuo or when heated to around 100C.
Chemists in those days often reported how the compounds that they had prepared
tasted. Zeise described the taste of this potassium salt as metallic, astringent and long
lasting.
DietmarSeyferth,Organometallics,2001,20,2
First bondedOrganometallicCompound Diethylzinc
3C2H5I+3Zn (C2H5)2Zn+C2H5ZnI+ZnI2
EdwardFrankland StudentofRobertBunsen(Bunsenburner
18251899 fame!).Prepareddiethylzincwhiletryingto
makeethylradicals.
Franklandcoinedthe
term
Organometallic
220- 250 C
Ni(s) + 4 CO Ni(CO)4 (g) bp 42 C
Ni Fe
C C C C
C C C C
O O O O
O O O O O
Ni(CO)4 Fe(CO)5
18901930textbooks
Mo(CO)6
TheGrignardReagent
FranoisAuguste
VictorGrignard 1871
1935
HaptoligandsandSandwichcompounds
(5C5H5)2Fe (6C6H6)2Cr
H
FeCl3 + CpMgBr
Fe
Kealy and Pauson
H
Fe + Cp H
Miller, Tebboth and Tremaine Fe+2
H Kealy
Pauson expectedfulvalene
A newtypeoforganoironcompound,Nature1951
Dicyclopentadienyl iron,J.Chem.Soc.,1952
Ferrocene
Fe
1973NobelPrize
G.Wilkinson E.O.Fischer R.B.Woodward
sandwichcompounds 1965NobelPrize
artoforganicsynthesis
Wilkinson,Rosenblum,Whitney,Woodward,J.Am.Chem.Soc.,1952
Ferrocene:Fueladditive,smokesuppressantandchiral catalystprecursor
R
CH CH2
OttoRoelen H HC
PioneerinIndustrial
O FirstIndustrialplant hydroformylation
homogeneouscatalysis
(18971993)
O
H
O
O O
O
diethylhexylphthalate [DEHP]
Plasticizer
detergents
Organometallic catalystsinindustrialsynthesis:
ThreeNobelPrizes2000,2005and2010
Hydrogenation
Methanoltoaceticacidprocess
CH3OH + CO CH3COOH
Olefinpolymerizationandoligomerization
* * *
*n *n *n
Isotactic polypropylene Syndiotactic polypropylene Atactic polypropylene
C4-C8 40%
n C10- C18 40 %
C20 & > 20 %
18electronrule:Howtocountelectrons
Therulestatesthatthermodynamicallystabletransitionmetalorganometallic compounds
areformedwhenthesumofthemetaldelectronsandtheelectronsconventionally
consideredasbeingsuppliedbythesurroundingligands equals18.
Ingeneral,theconditionsfavouringadherencetothe18electronruleare,anelectronrich
metal(onethatisinalowoxidationstate)andligandsthataregoodacceptors
Thehaptosymbol,, withanumericalsuperscript,providesatopologicaldescription
byindicatingtheconnectivitybetweentheligandandthecentralatom.Forexample,
ifallthefivecarbonatomsofacyclopentadienylmoietyareequidistantfromametal
atom,wetermitas5cyclopentadienyl
Examples:
1R,1Ar2C2R4 1allyl,3allyl,4 Cb,5Cp,6C6H6 8C8H8 2C60,5
R5C60.
Examples:
2CO,3CO,2CH3,2H,2Cl,,3Cl,2OR,2PR2,2NR2
Methodsofcounting:Neutralatommethod&Oxidationstatemethod