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Colorsoftransitionmetalcomplexes:

. IntensityofColor

Howintensityofcolorisexpressed

The molar absorption coefficient, molar extinction coefficient,


or molar absorptivity (), is a measurement of how strongly a chemical
species absorbs light at a given wavelength. It is an intrinsic property of
the species; the actual absorbance A, of a sample is dependent on the
pathlength, , and the concentration, c, of the species via the Beer
Lambert law,
Selectionrules:
ElectronictransitionsinacomplexaregovernedbySelectionrules

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

Practical significance of the Spin Selection rule


Duringanelectronictransition,theelectronshouldnotchangeitsspin

d5Highspin(e.g [Mn(H2O)6]2+

eg eg

[GS] [ES] [GS] [ES] t2g t2g

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

Transitiontype Example Typicalvaluesof/m2mol1

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

KMnO4 PrussianBlueFerricThiocyanate Pot.Dichromate


Whathappensiftheabsorptionofelectromagneticradiationforan
octahedralcomplexfallsintheultravioletrange?

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

Arrange the given metal complexes in the


increasing order of intensity of color () shown by
them. Justify your order by writing below each the
status of the selection rules for these complexes
(no partial marks) [
F
Fe4[Fe(CN)6]3 , [CoBr4]2, [MnF6]4, [Co(H2O)6]2+

Least intense Most intense

Spin Forbidden Spin Allowed Spin Allowed Spin Allowed


Laporte Allowed
Laporte Forbidden Laporte
Laporte Allowed Charge Transfer
Forbidden (Tetrahedral) transition
OrganometallicChemistry

Anareawhichbridgesorganicandinorganicchemistry
Abranchofcoordinationchemistrywherethecomplexhasoneor
more metalcarbonbonds

Themetalligandinteractionsaremostly acidtype
MCbondcanbea typeor typebond

C C
M M *
C C

donation from back donation to *

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

K[(C2H4)PtCl3]. H2O + KCl

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

As the early 1850s English chemist Edward Frankland described flasks


exploding, throwing bright green flames across his lab, as he heroically
distilled dialkylzinc compounds under an atmosphere of hydrogen.
Metalcarbonyls

The Mond process of Nickel purification


200 C
NiO + H2 ( from Syn gas) Impure Ni ( Fe and Co) + H2O
excess CO
50 -60 C

220- 250 C
Ni(s) + 4 CO Ni(CO)4 (g) bp 42 C

LudwigMond18391909 Ni(CO)4, Fe(CO)5, Co2(CO)8, Mo(CO)6


1890 1891 1910
FatherofMetalCarbonylChemistry
FounderofImperialChemicalIndustry,
Mondnickelcompanywasmakingover3000tonsofnickel
England in1910withapuritylevelof99.9%

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

He was the student of Philippe Barbier (Barbier reaction


[Zn]) He discovered the Grignard reaction [Mg]) in 1900. He
became a professor at the University of Nancy in 1910 and
was awarded the Nobel Prize in Chemistry in 1912.

FranoisAuguste
VictorGrignard 1871
1935
HaptoligandsandSandwichcompounds

The hapto symbol, , with a numerical superscript, provides a topological


description by indicating the number of carbon atoms at a bonding distance to
the metal
Sandwich

(5C5H5)2Fe (6C6H6)2Cr

BentSandwich HalfSandwich Tripledecker


&polycyclic
Ferrocene:Pathbreaking discoveryofasandwichcompound

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

Ferrocenepowder Ferrocene crystals

Ferox Gas & Diesel Fuel


Additive is a catalyst that
is an ecofriendly fuel
additive and horsepower
booster. It allegedly
increases mileage from
between 10 and 20%
while also significantly
reducing harmful
emissions.
Firstorganometallics inhomogeneouscatalysis
TheHydroformylation (1938)
R
C CH2
H
HCo(CO)4 CO,
200 bar, H2
110C

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

RHC CH2 + H2 RCH2CH3

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.

Thesymbol indicatesbridgingnormallywehave2 andrarely3 bridging

Examples:
2CO,3CO,2CH3,2H,2Cl,,3Cl,2OR,2PR2,2NR2
Methodsofcounting:Neutralatommethod&Oxidationstatemethod

Ligand Neutral Oxidation state Ligand Neutral Oxidation state


atom atom
Electron Formal Electron Formal
contributi charge contribu charge
on tion
Carbonyl (MCO) 2 2 0 Halogen ( MX) 1 2 1
Phosphine (MPR3) 2 2 0 Alkyl (MR) 1 2 1
Amine (MNR3 ) 2 2 0 Aryl (MAr) 1 2 1
Amide (MNR2 ) 1 2 1 acyl (MC(O)R 1 2 1
Hydrogen (MH) 1 2 1 1-cyclopentadienyl 1 2 1
Alkene (sidewise) 2- 2 2 0 1-allyl 1 2 1
Alkyne (sidewise) 2- 2 2 0 3-allyl 3 4 1
2-C60 2 2 0 5-cyclopentadienyl 5 6 1
Nitrosyl bent 1 2 1 6-benzene 6 6 0
Nitrosyl linear 3 2 +1 7-cycloheptatrienyl 7 6 +1
Carbene (M=CR2) 2 4 2 Carbyne (MCR) 3 6 3
Alkoxide (MOR) 1 2 1 Thiolate (MSR) 1 2 1
-CO (M(CO)M) 2 2 0 -H 1 2 1
-alkyne 4 4 0 -X (MXM) 3 4 1
X = halogen
-alkyl 1 2 1 -amido 3 4 1
(M(NR2)M
-phosphido 3 4 1 -alkoxide 3 4 1
(M(PR2)M (M(OR)M