Multiple Bonds between Transition Metals and “Bare” Main Group Elements: Links between Inorganic Solid State Chemistry and Organometallic Chemistry

Abstract The last two decades have seen a dramatic development in the study of metal‐metal multiple bonds, particular successes being recorded in the field of organometallic chemistry. Syntheses designed to produce novel transition metal complexes with single, double, triple and quadruple metal‐metal bonds occupy a most important place in such research, as also do reactivity studies. A striving to establish general principles has provided much of the motivation for such work, but one less obvious goal—the commercial application of the catalytic properties of metal‐metal multiple bonding systems, in the medium and long term—should not be overlooked. All aspects of the investigations of metal‐metal multiple bonds also apply to a particular class of compound that has, however, enjoyed little lime‐light and thus deserves the present review: complexes with multiple bonds between transition metals and substituent‐free (“bare”) main group elements. Although based mostly on accidental discoveries, the few noteworthy examples are now beginning to unfold general concepts of synthesis that are capable of being extended and thus are deserving of exploitation in preparative chemistry. The availability of further structural patterns exhibiting multiple bonds between transition metals and ligand‐free main group elements might enable preparative organometallic chemistry to expand in a completely new direction (for instance by the stabilizing or activation of small molecules at the metal complex). This essay discusses the chemistry of complexes of bare carbon, nitrogen, and oxygen ligands (carbido‐, nitrido‐, and oxo‐complexes) and their relationships to higher homologues from both a synthetic and a structural point of view.