Selectivity Effects in Bimetallic Catalysis

• Published in: Chemistry : a European journal Vol. 22; no. 17; pp. 5822 - 5829
• Main Author: Mankad, Neal P.
• Format: Journal Article
• Language: English
• Published: Germany Blackwell Publishing Ltd 18.04.2016; Wiley Subscription Services, Inc
• Subjects: Bimetals; Case studies; Catalysis; Catalysts; Chemistry; Compatibility; cooperative effects; Electronic properties; heterometallic complexes; homogeneous catalysis; Ligands; metal-metal interactions; Metals; Optimization; organometallic chemistry; Selectivity; Stereoselectivity; Transformations; metal-metal interactions; heterometallic complexes; homogeneous catalysis; cooperative effects; organometallic chemistry
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201505002

An emerging area of homogeneous catalysis is the use of catalysts featuring two closely associated metal sites. This approach complements the traditional focus on single‐site catalysts and makes available new parameters with which to optimize catalytic behavior. Single‐site catalysts are optimized through changing 1) the identity of the metal, and 2) the steric and electronic properties of the ligands. Bimetallic catalysts introduce new optimization parameters such as 3) catalyst nuclearity (mononuclear vs. binuclear), and 4) bimetallic pairing (relative compatibility of two metal sites). In order to harness these new optimization parameters in developing systems, it is necessary to first understand the origin of bimetallic selectivity effects that already have been documented. This Concept article highlights bimetallic effects on the chemo‐, regio‐, and stereoselectivity of catalytic transformations, using selected case studies from the recent literature as illustrative examples. It takes two! The effects of catalyst nuclearity on catalytic chemo‐, regio‐, and stereoselectivity are explored through examination of recent case studies. Collectively, these studies show that catalyst nuclearity is complementary to ligand design as a potential optimization parameter in homogeneous catalysis.