Group 5 Imides and Bis(imide)s as Selective Hydrogenation Catalysts

Abstract

AbstractIn this microreview, we focus on our work on the development of group 5 imido and bis(imido) semihydrogenation catalysts in the context of previous stoichiometric studies on d0 metal–ligand multiple‐bond activations of strong σ bonds and both stoichiometric and catalytic studies on H2 activation and hydrogenation by d2 group 5 complexes. These studies develop electronic structure models and mechanistic analyses necessary for the application of catalytic reactions involving 1,2‐addition reactions of σ‐bonded substrates across early transition metal–ligand multiple bonds. Extension of these studies to the second and third row group 5 imido complexes has led to the development of mechanistically distinct hydrogenation catalysts with product selectivities not readily obtainable with traditional late transition‐metal catalysts that employ H2 as the reductant.