Boratabenzene Derivatives of Divalent Samarium: Syntheses, Structures and Catalytic Reactivities of (C5H5BXPh2)2Sm(THF)2 (X = N, P)

摘要

The preparation and characterization of the complexes (C5H5BXPh2)2Sm(THF)2 (X = N (1), P (2)), the first boratabenzene derivatives of a divalent lanthanide metal, are reported. Their solid-state structures display different structural features arising from the different degrees of B—X pi interactions. Complexes 1 and 2 initiate the polymerization of methyl methacrylate (MMA) to a highly syndiotactic and atactic PMMA, respectively. Organolanthanide complexes promote a variety of useful transformations such as hydrogenation, hydroamination, hy-drosilylation, hydrophosphination, olefin and polar monomer polymerizations, reductions, and reductive-coupling reactions. The most widely investigated organolanthanides are those bearing Cp-type ligands. Our group's longstanding interest in developing organolanthanide complexes has led us to prepare a new family of organolanthanides based on non-Cp ligands and to explore their reactivities. Our current efforts are concerned with the derivatives of boratabenzenes.