C- and O-Bonded Metal Carbonyls: Formation, Structures, and Reactions

Abstract

Publisher Summary Metal carbonyls, which were among the earliest discovered organometallic compounds, continue to play a central role in organometallic chemistry. Carbonyl basicity is found for C-bridging CO ligands in metal–metal bonded compounds, CO ligands in anionic metal carbonyls, or CO ligands in donor-substituted metal carbonyls. The interaction of protons with mononuclear metal carbonyls readily occurs at the metal center rather than the CO oxygen; no stable or transient MCO–H species appear to have been observed. The chemical and structural characterization of molecular compounds containing π–CO is of great interest, because the π–CO is implicated as a precursor to the cleavage of CO on metal surfaces, such as those employed in Fischer–Tropsch catalysis. In view of these large physical changes, it perhaps is not surprising that C and O bonding also engenders large changes in CO reactivity. Carbon monoxide insertion into a metal–alkyl bond is a fundamental reaction in organometallic chemistry as well as an important step in the commercial production of oxygen-containing organics, such as aldehydes and acetic acid.