| Abstract: | Conformational preferences of two classes of organometal complexes have been surveyed by inspecting the Cambridge Structural Database (CSD). Lewis acid carbonyl complexes demonstrate a variety of coordination geometries, depending on the electronic and steric requirements of the carbonyl ligands and the nature of the Lewis acid. Similarly, the solid-state conformation of various π-bonding ligands in metal acyl, metal nitrosyl, metal acetylene, and metal imido complexes is revealed. These insights have stimulated the development of a conformational model that is based on considerations of π-bond hybridization and frontier molecular orbital theory. The analyses are relevant to the mechanism and transition structures of many synthetically important transformations. A deeper understanding of the conformational properties of organometal complexes, based on accurate structural information, will likely expedite the design and improvement of metal-mediated processes. |
