Mono-, di- and tri-metallic complexes of trimethylenemethane: an EHMO study of the TMM rotational barrier (original) (raw)

Journal of Organometallic Chemistry, 1994

Abstract

Abstract The rotational barrier of a trimethylenemethane ligand relative to an Fe(CO) 2 L unit, where L  CO or a phosphine, is analyzed by molecular orbital calculations at the extended Huckel level. It is shown that the original Hoffmann-Albright model fits well for carbonyl complexes, but yields barriers for phosphine complexes that are too high. A rationale is presented to account for the different behavior of the bimetallic complexes Cp 2 M′M″(CO) 2 (TMM), where M′ M″ Ru, 2 , (trimethylenemethane (TMM) non-fluxional), and for M′ W and M″  Ni, 3 , where the TMM rotates. Finally, calculations reveal that the trimetallic complex [(TMM)CO 3 (CO) 9 ] + should be a stable and non-fluxional system with an eclipsed conformation.

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