18-Electron Rule - Applicability of The 18-electron Rule

Applicability of The 18-electron Rule

Although the majority of metal complexes do not satisfy the 18-electron rule, the rule usefully predicts the formulae for low-spin complexes of the Cr, Mn, Fe, and Co triads. Well-known examples include ferrocene, iron pentacarbonyl, chromium carbonyl, and nickel carbonyl.

Ligands in a complex determine the applicability of the 18-electron rule. In general, complexes that obey the rule are composed at least partly of π-acid ligands. This kind of ligand exerts a very strong ligand field, which lowers the energies of the resultant molecular orbitals and thus favorably occupied. Typical ligands include olefins, phosphines, and CO. Complexes of π-acids typically feature metal in a low-oxidation state. The relationship between oxidation state and the nature of the ligands is rationalized within the framework of π backbonding.