Transition metal hydride and main-group element complexes in new ligand environments

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Transition metal hydrides, compounds with a metal-hydrogen bond, are indispensable in chemistry due to their relevance to the whole range of catalytic industrial hydride transfer processes, including the production of both commodity chemicals and fine chemicals, and in laboratory applications to make a large range of derivatives. Whereas industrial catalysts are primarily heterogeneous with a poorly defined nature of reactive intermediates, laboratory homogeneous catalysts feature very well-defined reactive sites (usually based on one, two or few metal centres) supported by ancillary groups of controllable electronic and steric properties. Until very recently, the vast majority of established hydride complexes were based solely on the abundant phosphine, carbonyl, and polyolefin ligand environments, while relatively little is known about the reactivity of hydride complexes supported by new generations of nitrogen-based ligands. Such new ligands and ligand combinations are now well established, but almost exclusively in the narrow context of homogeneous olefin polymerization catalysis.