Bimetallic Catalysis using Transition and Group 11 Metals: An Emerging Tool for CC Coupling and Other Reactions

Bimetallic catalysis refers to homogeneous processes in which either two transition metals (TM), or one TM and one Group 11 (G11) element (occasionally Hg also), cooperate in a synthetic process (often a CC coupling) and their actions are connected by a transmetalation step. This is an emerging research area that differs from the isolated or tandem applications of the now classic processes (Stille, Negishi, Suzuki, Hiyama, Heck). Most of the reactions used so far combine Pd with a second metal, often Cu or Au, but syntheses involving very different TM couples (e.g., Cr/Ni in the catalyzed vinylation of aldehydes) have also been developed. Further development of the topic will soon demand a good knowledge of the mechanisms involved in bimetallic catalysis, but this knowledge is very limited for catalytic processes. However, there is much information available, dispersed in the literature, coming from basic research on exchange reactions occurring out of any catalytic cycle, in polynuclear complexes. These are essentially the same processes expected to operate in the heart of the catalytic process. This Review gathers together these two usually isolated topics in order to stimulate synergy between the bimetallic research coming from more basic organometallic studies and the more synthetic organic approaches to this chemistry. Two are better than one: Bimetallic catalysis, combining the action of at least two non‐main‐group metals for the formation of CC bonds and other reactions, has been quietly growing in very recent years. Pd and Cu or Au initially dominated the topic, but other metals are joining the feast (see figure). This review brings together knowledge coming from classic inorganic and organometallic studies on polymetallic systems and the newer studies in the field of bimetallic catalysis.