ON THE CONFORMATION AND STRUCTURE OF ORGANOMETAL COMPLEXES IN THE SOLID-STATE - 2 STUDIES RELEVANT TO CHEMICAL SYNTHESIS

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. Copyright © 1990 by VCH Verlagsgesellschaft mbH, Germany