Homogeneously catalyzed hydrogenation and dehydrogenation reactions – From a mechanistic point of view

Abstract Homogeneously catalyzed hydrogenation/dehydrogenation reactions represent not only one of the most synthetically important chemical transformations, but also a promising way to renewably utilize the hydrogen energy. In order to rationally design efficient homogeneous catalysts for hydrogenations/dehydrogenations, it is of fundamental importance to understand their reaction mechanisms in detail. With this aim in mind, we herein provide a brief overview of the mechanistic understanding and related catalyst design strategies. Hydrogenations and dehydrogenations represent the reverse process of each other, and involve the activation/release of H 2 and the insertion/elimination of hydride as major steps. The mechanisms discussed in this chapter include the cooperation (bifunctional) mechanism and the non-cooperation mechanisms. Non-cooperation mechanisms usually involve single-site transition metal (TM) catalysts or transition metal hydride (TM-H) catalysts. Cooperation mechanisms usually operate in the state-of-the-art bifunctional catalysts, including Lewis-base/transition-metal (LB-TM) catalysts, Lewis-acid/transition-metal (LA-TM) catalysts, Lewis-acid/Lewis-base (LA-LB; the so-called frustrated Lewis pairs - FLPs) catalysts, newly developed ambiphilic catalysts, and bimetallic transition-metal/transition-metal (TM-TM) catalysts. The influence of the ligands, the electronic structure of the metal, and proton shuttle on the reaction mechanism are also discussed to improve the understanding of the factors that can govern mechanistic preferences. The content presented in this chapter should both inspire experimental and theoretical chemists concerned with homogeneously catalyzed hydrogenation and dehydrogenation reactions, and provide valuable information for future catalyst design.