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
atom

Oxidation state
Electron
contributi
on

Formal
charge

Ligand

Neutral
atom

Oxidation state
Electron
contribu
tion

Formal
charge

Carbonyl (MCO)

Halogen ( MX)

Phosphine (MPR3)

Alkyl (MR)

Amine (MNR3 )

Aryl (MAr)

Amide (MNR2 )

acyl (MC(O)R

Hydrogen (MH)

1-cyclopentadienyl

Alkene (sidewise) 2-

1-allyl

Alkyne (sidewise) 2-

3-allyl

5-cyclopentadienyl

Nitrosyl bent

6-benzene

Nitrosyl linear

+1

7-cycloheptatrienyl

+1

Carbene (M=CR2)

Carbyne (MCR)

Alkoxide (MOR)

Thiolate (MSR)

-CO (M(CO)M)

-H

-alkyne

-X (MXM)
X = halogen

-alkyl

-amido
(M(NR2)M

-phosphido
(M(PR2)M

-alkoxide
(M(OR)M

2-C60

CO
Ru

PPh3

PPh3

N
Fe

Ru
3- allyl
2 PPh3
CO
charge

neutral atom
method
8

Me
Me

Fe
2 5-Cp

3
4
2
-1
16
8

oxidation state
method
6 (Ru +2)
4
4
2
not required

16

10

6 (Fe +2)
12

18

18

Neutralatommethod:Metalistakenasinzerooxidationstateforcountingpurpose
Oxidationstatemethod:Wefirstarriveattheoxidationstateofthemetalbyconsideringthe
numberofanionicligands presentandoverallchargeofthecomplex
Suggestion:Focusononecountingmethodtillyouareconfident

Easywaytorememberligand electroncontributionforneutralatomcountingmethod
Electroncontribution

Neutralterminal: CO,PR3,NR3
Anionicterminal: X,H,R,Ar,R2N,R2P,RO
Haptoligands
:2C2R4 2C2R2,4C2R2 ,1allyl,
3allyl,4 Cb,5Cp,6C6H6
7C7H7 8C8H8 2C60,5R5C60
bridgingneutral 2CO,3CO
Bridginganionic 2CH3,2H
(nolonepairs)

2 electrons
1 electron

sameashapticity
2 electrons
1 electron

Bridginganionic 2Cl,,2OR,2PR2,2NR2
(with1lonepair)
3Cl(2l.p)

3 electrons

Bridgingalkyne

4electrons

NOlinear

3electrons

NObent (l.ponnitrogen)

1electron

CarbeneM=C

2electron

CarbyneMC

3electron

5electrons

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
(A)

Fe3(CO)12

48

(18 n) A
(B)

54 48 = 6

Total MM
bonds (B/2)

Bonds per metal

6/2 = 3

48/3 = 16; 2

Basic geometry of
metal atoms

Fe

Fe
Fe

Co4(CO)12

60

72 60 = 12

12/2 = 6

Co

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

Ni
OC

OC

CO
CO

Mn

OC
OC

CO

Mn

CO

CO Os

OC

Os
OC

CO

CO
CO
O
C

OC

Co

OC

CO
CO

CO

Os
CO
CO

OC
OC
OC

CO

Co

CO
CO

C
O
OC

CO
CO

OC

OC
CO

CO

Cr

CO

CO OC

OC

OC

CO
CO

CO OC

OC

Fe

CO

Ir

CO
CO
CO

Ir
OC
OC

Ir
Ir

CO
CO

CO

Coordinationnumberaroundthemetalnormallyremainssixorlesser.
speciessuchasMn(CO)5,Co(CO)4 dimerize togain18electrons
V(CO)6 doesnotdimerize.

17electron

AJELIASL2S2

Whystudymetalcarbonyls?
SimplestoforganometalliccompoundswhereMC bondingiswellunderstood. COisone
ofthestrongest acceptor ligands.Backbonding( bonding)andvariationinelectronic
propertiesofCOcanbemonitoredveryefficientlybyInfraredspectroscopy

ArangeofmetalcarbonylsareusedascatalystsinChemicalIndustry

MethanoltoAceticacid
Process

Hydroformylation
AlkenetoAldehyde
R
C

CH 2

HCo(CO)4
R

CH
H

MeOH + HI
MeI

CO,
H2

H3C C

CH 2
HC

O
O

MeI + H2O
CO

[Rh(CO)2I2]
H2O

H3C C
O
H3C C
O

OH

AJELIASL2S3
*

MolecularOrbitaldiagramofCO
WhydoesCObindametalthroughitsless
electronegativecarbonatomthanitsmore
electronegativeoxygen?Whatmakesita
good acceptor?
The highest occupied molecular orbital
(HOMO) of CO is weakly antibonding
(compared with the O atomic orbitals)
and is an MO which is carbon based.
Secondly, the * antibonding orbital
which is the lowest unoccupied
molecular orbital (LUMO) is also of
comparatively lower energy which makes
it possible to interact with metal t2g
orbitals for bonding. There exists a
strong back bonding of metal electrons
to the * antibonding orbitals of CO

*
LUMO

2p
10.7 ev

HOMO

2p
15.9 ev

2s
19.5 ev

CO

2s
32.4 ev

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

OC
OC
OC

CO OC CO

Mn

Mn

CO

Therangeinwhich
thebandappears
decidesbridgingor
terminal.

CO

CO OC

terminal

Thenumberof
bandsisonly
relatedtothe
symmetryofthe
molecule

OC
OC
OC

O
C

O
C

Fe

CO

Fe
C
O

CO
CO

terminal

bridging