Professional Documents
Culture Documents
Therulestatesthatthermodynamicallystabletransitionmetalorganometallic compounds
areformedwhenthesumofthemetal delectronsandtheelectrons
conventionallyconsideredasbeingsuppliedbythesurroundingligands
equals18.
Ingeneral,theconditionsfavoringadherencetothe18electronruleare,anelectronrichmetal
(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
Neutralatommethod:Metalistakenasinzerooxidationstateforcountingpurpose
Oxidationstatemethod:Wefirstarriveattheoxidationstateofthemetalbyconsideringthe
numberofanionicligands presentandoverallchargeofthecomplex
Suggestion:Focusononecountingmethodtillyouareconfident
Easywaytorememberligand electroncontributionforneutralatomcountingmethod
Electroncontribution
Neutralterminal: CO,PR3,NR3 2 electrons
Anionicterminal: X,H,R,Ar,R2N,R2P,RO 1 electron
Haptoligands :2C2R4 2C2R2,4C2R2 ,1allyl,
3allyl,4 Cb,5Cp,6C6H6
7C7H7 8C8H8 2C60,5R5C60 sameashapticity
bridgingneutral 2CO,3CO 2 electrons
Bridginganionic 2CH3,2H (nolonepairs) 1 electron
Bridgingalkyne 4electrons
NOlinear 3electrons
CarbeneM=C 2electron
CarbyneMC 3electron
Howtodeterminethetotalnumberofmetal metalbonds
Determinethetotalvalenceelectrons(TVE)intheentiremolecule(thatis,thenumberofvalence
electronsofthemetalplusthenumberofelectronsfromeachligand andthecharge);say,itisA.
(a) B dividedby2givesthetotalnumberofMMbondsinthecomplex.
Fe
Co
Co4(CO)12 60 72 60 = 12 12/2 = 6 60/4 = 15; 3
Co Co
Co
Understandingmetalmetalbondelectroncountbecomeeasierifyoucompare
andseehowoctetisattainedbyeachCl atomofCl2
Exceptionstothe18electronrule
Squareplanarorganometallic complexesofthelatetransition
metals(16e).
Somehighvalent d0 complexeshavealowerelectroncount
than18.
The18electronrulefailswhenbondingoforganometallic clustersof
moderatetobigsizes(6Metalatomsandabove)areconsidered.
CO CO CO
CO OC CO
Ni OC Fe Cr
CO OC CO
OC CO
CO
CO CO
O
CO OC CO C CO
OC OC
OC Mn Mn CO
OC Co Co CO
OC CO OC CO
CO OC C
O
CO
OC
CO CO
OC CO Ir
OC
CO Os CO CO
OC
OC CO Ir Ir
OC CO
Os Os Ir CO
OC CO CO OC
OC CO
CO CO
Coordinationnumberaroundthemetalnormallyremainssixorlesser. 17electron
speciessuchasMn(CO)5,Co(CO)4 dimerize togain18electrons
V(CO)6 doesnotdimerize.
AJELIASL2S2
Whystudymetalcarbonyls?
ArangeofmetalcarbonylsareusedascatalystsinChemicalIndustry
Hydroformylation MethanoltoAceticacid
AlkenetoAldehyde Process
R
C CH 2
MeOH + HI MeI + H2O
H
CO H3C C I
CO, MeI
HCo(CO)4 H2 [Rh(CO)2I2] O
R H2O
H3C C I H3C C OH
CH CH 2
O O
H HC
O
AJELIASL2S3
*
MolecularOrbitaldiagramofCO
WhydoesCObindametalthroughitsless *
LUMO
electronegativecarbonatomthanitsmore
electronegativeoxygen?Whatmakesita
good acceptor? 2p
10.7 ev
The highest occupied molecular orbital HOMO
(HOMO) of CO is weakly antibonding
(compared with the O atomic orbitals)
and is an MO which is carbon based.
Secondly, the * antibonding orbital
2p
which is the lowest unoccupied 15.9 ev
molecular orbital (LUMO) is also of
comparatively lower energy which makes
it possible to interact with metal t2g
orbitals for bonding. There exists a *
2s
strong back bonding of metal electrons 19.5 ev
Countingtheelectronshelpstopredictstabilityofmetalcarbonyls.Butitwillnot
tellyouwhetheraCOisbridgingorterminal
AJELIASL2S5
InfraredSpectroscopy Aspectroanalyticaltoolinchemistry
Infrared (IR) spectroscopy is one of the most common spectroscopic techniques used by organic
and inorganic chemists. Simply, it is the absorption measurement of different IR frequencies by a
compound positioned in the path of an IR beam. The main goal of IR spectroscopic analysis is to
determine the chemical functional groups in the sample. Functional groups are identified based
on vibrational modes of the groups such a stretching, bending etc. Different vibrational modes
absorb characteristic frequencies of IR radiation. An infrared spectrophotometer is an
instrument that passes infrared light through a molecule and produces a spectrum that contains
a plot of the amount of light transmitted on the vertical axis against the wavelength of infrared
radiation on the horizontal axis. Absorption of radiation lowers the percentage transmittance
value.
AJELIASL2S6
InfraredSpectroscopy SpectraofMetalCarbonyls
CO OC CO
OC
OC Mn Mn CO
OC CO Therangeinwhich
CO OC
thebandappears
decidesbridgingor
terminal
terminal.
Thenumberof
bandsisonly
relatedtothe
symmetryofthe
molecule
O O bridging
OC C C CO
OC Fe Fe CO
OC C CO
O
terminal