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The reactivity of polynuclear metal complexes involving metal-metal bonds with simple inorganic and organic molecules is considered. The basic structural forms of polynuclear aggregates is reviewed and the fluxional nature of polynuclear carbonyls is surveyed. The use of 13C n.m.r. spectroscopy in determining the mechanism of fluxional interchange within the polynuclear carbonyls of Group VIII elements is described and the variety of pathways for exchange of carbonyl groups on a given metal centre or between different metal centres is established and correlated with the structure of the polynuclear species. As the majority of structures of polynuclear carbonyls are based on triangular faced polyhedra, the dodecacarbonyls of iron, ruthenium and osmium have been used as the simplest model for considering the interaction of inorganic and organic molecules with a polynuclear aggregate. The general facility of polynuclear metal species in accepting or donating electrons (i.e. electronic amphoteric behaviour) is related to their orbital structure and their ready interaction, involving a variety of bonding patterns, with simple inorganic molecules is reviewed. The considerable facility for hydrogen abstraction is emphasized and the chemistry of the substituted hydridocarbonyls described. For simple alkenes and alkynes, a number of bonding patterns have been established, with bonding to two or three metal atoms of the cluster unit. For alkenes, interaction occurs with fission of carbon-hydrogen bonds and the formation of metal-hydrogen and metal-carbon bonds. The relationship between the coordinated organic fragment and the product of interaction of the polynuclear groupings with alkynes is established. An analogy between the behaviour of these unsaturated species with polynuclear carbonyls and the interaction of alkenes and alkynes with metal surfaces is emphasized.

Reactions of simple unsaturated molecules with the polynuclear carbonyls of some Group VIII elements