Group 5 imides and bis(imide)s as selective hydrogenation catalysts

In 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 involving1, 2-addition reactions of s-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.