Non-precious Metal Complexes with an Anionic PCP Pincer Architecture

This perspective article provides an overview of the advancements in the field of non-precious metal complexes featuring anionic PCP pincer ligands with the inclusion of aliphatic systems. It covers research from the beginning in 1976 until late 2015 and provides a summary of key developments in this area, which is, to date, limited to the metals nickel, cobalt, iron, and molybdenum. While the research in nickel PCP complexes is already quite extensive, the chemistry of cobalt, iron, and molybdenum PCP complexes is comparatively sparse. With other non-precious metals such as copper, manganese, chromium or vanadium no PCP complexes are known as yet. In the case of nickel PCP complexes already many catalytic applications such as Suzuki-Miyaura coupling, C-S cross coupling, Kharasch and Michael additions, hydrosilylation of aldehydes and ketones, cyanomethylation of aldehydes, and hydroamination of nitriles were reported. While iron PCP complexes were found to be active catalysts for the hydrosilylation of aldehydes and ketones as well as the dehydrogenation of ammonia-borane, cobalt PCP complexes were not applied to any catalytic reactions. Surprisingly, only one molybdenum PCP complex is reported, which was capable of cleaving dinitrogen to give a nitride complex. This perspective underlines that the combination of cheap and abundant metals such as nickel, cobalt, and iron with PCP pincer ligands may result in the development of novel, versatile, and efficient catalysts for atom-efficient catalytic reactions.