Nomenclature

Ligands may bond with metals through different atoms.

Classified based on hapticity (h or η)
Derived from Greek word – “Fasten”

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 Hapticity
• Number of carbon atoms of an organic moiety
linked to the metal.

• Mono-hapto (h1 or η1) – one carbon linked to

metal

• h2 – two carbon atoms linked etc.,

 Hapticity

η1

η1 η3
 Hapticity

• Ferrocene?

h
 Hapticity
• bis(η8-1,3,5,7-cyclooctatetraene)uranium
• Tris(h3allyl)chromium(III)
• (h4butadiene)tricarbonyliron(0)
• Dichlorobis(h5cp)titanium(IV)
• Tricarbonyl(h7cycloheptatrienyl)molebdenum(0)
• Chloro(h1,h3cp)cobalt(II)
 Simple OMT compounds
• Written in one word- name of org. group
followed by name of the metal.

• Diphenylmercury Ph-Hg-Ph
• Hexaphenyldisilane Ph3-Si-Si-Ph3
• Trimethyltinacetate Me3-Sn-OAc
• Butyllithium (Bu-Li-Bu)n
 Bridging ligands
• designated by the prefix μ, followed by a
subscript indicating the number of metal
atoms bridged.
• Homoleptic – same type
ligand

• Heteroleptic – Different
type ligand
 References
• Organometallic Chemistry – G.S.Sodhi

• Organometallic chemistry – R.C.Mehrotra

• Inorganic Chemistry – Meissler Tarr

 18 electron rule
• used primarily for predicting and rationalizing
formulae for stable metal complexes, especially
organometallic compounds.

• first proposed by American chemist Irving

Langmuir in 1921

• OCTET RULE – main group elements

• The 18-electron Rule is based on a similar

concept.
 18 electron rule

• The central TM can accommodate electrons in the s, p, and d

orbitals.

• s (2) , p (6) , and d (10) = maximum of 18

• This means that a TM can add electrons from Lewis Bases (or
ligands) in addition to its valence electrons to a total of 18.

• This is also known Effective Atomic Number (EAN) Rule

 EAN Summary
• Works well only for d-block metals.

• Works best for compounds with TMs of low ox. state.

• Ligands which are good σ-donors and π-acceptors utilize all the valence orbitals
and thus such compounds obey this rule.

• Complexes which contain a combination of σ-donors and π-acceptors conform

to this rule. (e.g. Cr(NH3)3(CO)3 , Cr(6-C6H6)(CO)3).

• Compounds which obey this rule are kinetically inert to substitution reactions.

• Exceptions to the rule occur at the two ends of the transition series where nd,
(n+1)s, and (n+1)p valence orbitals are less well matched in energy.
 Electron counting
• No. of metal valance e- + no. of e- donated by ligand = 18

• STABLE

• Two methods:

– Oxidation state / ionic method

– Neutral atom method.

 Oxidation State Electron Count
• neutral ligands (like NH3) are considered as neutral
molecules with 2 electrons for donation to the metal.

• Ligands like methyl (CH3 and Cl) are viewed as

anions….NOT AS NEUTRAL RADICALS. (By
definition H is viewed as H-)

• After removal of the ligands the metal is assigned a

formal charge
 Neutral atom method
• REMOVE ALL THE LIGANDS FROM THE METAL AS NEUTRAL
SPECIES.

• This approach results in no difference for neutral ligands like NH3 or CO.

• BUT
• For ligands such as methyl we remove the ligand as a radical. It is therefore a
single electron donor in this model.

• Furthermore, in this model both the ligand and the metal must donate an
electron to the bond.
Examples
unstable
 Prediction of Structure.
• Co2(CO)8

A B

both are stable and exist as isomers.

Worked examples
 Exceptions to 18 e- rule
• ZrCl2(C5H5)2 4 +2+10 = 16
• TaCl2Me3 5+2+3 = 10
• WMe6 6+6 = 12
• Pt(PPh3)3 10+6 = 16
• IrCl(CO)(PPh3)2 9+1+2+4 = 16

• Reasons:
• Early transition metals (Zr, Ta, W)
• Several bulky ligands (PPh3)
• Square planar d8 e.g. Pt(II), Ir(I) (16 e- rule)
• σ-donor ligands (Me)