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18electronrule:Howtocountelectrons

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.

Thesymbol indicatesbridging;normallywehave2 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
neutral atom oxidation state
method method
CO Ru 8 6 (Ru +2)
PPh3
Ru 3- allyl 3 4
2 PPh3 4 4
PPh3
CO 2 2
charge -1 not required
16 16
Me
N Fe 8 6 (Fe +2)
Me
Fe 2 5-Cp 10 12
18 18

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

Bridginganionic 2Cl,,2OR,2PR2,2NR2 3 electrons


(with1lonepair)
3Cl(2l.p) 5electrons

Bridgingalkyne 4electrons

NOlinear 3electrons

NObent (l.ponnitrogen) 1electron

CarbeneM=C 2electron

CarbyneMC 3electron
Howtodeterminethetotalnumberofmetal metalbonds

Determinethetotalvalenceelectrons(TVE)intheentiremolecule(thatis,thenumberofvalence
electronsofthemetalplusthenumberofelectronsfromeachligand andthecharge);say,itisA.

Subtractthisnumberfromn 18wheren isthenumberofmetalsinthecomplex,thatis,(n 18) A;


say,itisB.

(a) B dividedby2givesthetotalnumberofMMbondsinthecomplex.

(b)A dividedbyn givesthenumberofelectronspermetal.Ifthenumberofelectronsis18,itindicates


thatthereisnoMMbond;ifitis17electrons,itindicatesthatthereis1MMbond;ifitis16
electrons,itindicatesthatthereare2MMbondsandsoon.

Molecule TVE (18 n) A Total MM Bonds per metal Basic geometry of


(A) (B) bonds (B/2) metal atoms

Fe3(CO)12 48 54 48 = 6 6/2 = 3 48/3 = 16; 2 Fe Fe

Fe
Co
Co4(CO)12 60 72 60 = 12 12/2 = 6 60/4 = 15; 3
Co Co

Co

[5-CpMo(CO) 2] 2 30 36 30 = 6 6/2 = 3 30/2 = 15; 3 MoMo

(4-C4H4)2Fe2(CO)3 30 36 30 = 6 6/2 = 3 30/2 = 15; 3 FeFe

Fe2(CO)9 34 36 34 = 2 2/2 = 1 34/2 = 16; 1 FeFe


Problemsolving
Thefollowingorganometallic compoundsarestableandhasa
secondrowtransitionmetalatitscentre.Findoutthemetaland
itsoxidationstate
Afewworkedoutexamples

Understandingmetalmetalbondelectroncountbecomeeasierifyoucompare
andseehowoctetisattainedbyeachCl atomofCl2
Exceptionstothe18electronrule

Squareplanarorganometallic complexesofthelatetransition
metals(16e).

Some organometallic complexes of the early transition metals


(e.g. Cp2TiCl2, WMe6, Me2NbCl3, CpWOCl3) [ A possible reason for
the same is that some of the orbitals of these complexes are too high in energy
for effective utilization in bonding or the ligands are mostly donors.]

Somehighvalent d0 complexeshavealowerelectroncount
than18.

Sterically demandingbulkyligands forcecomplexestohave


lessthan18electrons.

The18electronrulefailswhenbondingoforganometallic clustersof
moderatetobigsizes(6Metalatomsandabove)areconsidered.

Theruleisnotapplicabletoorganometallic compoundsof main


groupmetalsaswellastothoseoflanthanideandactinidemetals.
OML2S1
Metalcarbonyls

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?

SimplestoforganometalliccompoundswhereMC bondingiswellunderstood. COisone


ofthestrongest acceptor ligands.Backbonding( bonding)andvariationinelectronic
propertiesofCOcanbemonitoredveryefficientlybyInfraredspectroscopy

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

to the * antibonding orbitals of CO


2s
32.4 ev
C CO O
AJELIASL2S4

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