Abstract
The phenomenal growth in the chemistry of metal carbonyl compounds has been heavily concentrated upon the neutral and anionic complexes. The cationic metal carbonyls are, by definition, electrolytes in polar solvents, and are in general diamagnetic and conform to the rare gas formalism of metal carbonyls. The characteristic high carbonyl frequencies of cationic metal carbonyls are rationalized in terms of a reduced π-back-donation from the metal. Such a proposal implicitly assumes that the carbon-metal a-bond is independent of charge on the metal, and has been supported by semi-empirical molecular orbital calculations. The use of a Lewis acid to promote the abstraction of a halide anion from a metal halide complex, in the presence of a neutral ligand, has been widely employed to produce both substituted and totally unsubstituted metal carbonyl cations. The addition of a proton to a metal carbonyl compound may occur in either of two modes: the formation of metal–hydrogen bond, or protonation of a ligand attached to the central metal atom. If the ligand protonated is an organic radical, a carbonium ion is produced, which may be stabilized by suitable delocalization of charge over the complex, including the central metal atom.
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