ChemInform Abstract: Transition Metal Complexes with Terminal Carbyne Ligands

Abstract

Publisher Summary This chapter discusses the chemistry of molecular carbyne complexes; there is also much interest in them as models for species that are possibly present on metal surfaces in catalytic reactions. Surfacebound methine (CH) is a proposed intermediate in the Fischer–Tropsch synthesis, and alkylidyne groups are suggested as intermediates in heterogeneously catalyzed alkyne metathesis reactions. X-Ray structure determinations of carbyne complexes show that they have very short metal–carbon bond lengths consistent with a metal–carbon triple bond. In certain cases, ∞-protons of an alkylidene ligand may be abstracted by a base to give alkylidyne compounds. Addition of electrophiles to terminal isonitrile (CNR) ligands gives aminocarbyne complexes; the analogous reaction of terminal thiocarbonyl (CS) ligands gives thiocarbynes. Fischer and Himmelreich reported the abstraction of oxygen from an anionic carbamoyl compound with SOCl 2 to give an aminocarbyne compound. Reactions of cationic carbyne compounds with nucleophiles proceed exclusively by nucleophilic attack at the carbyne carbon atom, thus providing a synthetically useful route to certain carbene complexes. The field of transition-metal carbyne chemistry has matured to the point where a great deal is known about the structure, bonding, and reactivity of the carbyne ligand.