Metathesis by Partner Interchange in σ‐Bond Ligands: Expanding Applications of the σ‐CAM Mechanism

In 2007 two of us defined the σ‐Complex Assisted Metathesis mechanism (Perutz and Sabo‐Etienne, Angew. Chem. Int. Ed. 2007, 46, 2578–2592), that is, the σ‐CAM concept. This new approach to reaction mechanisms brought together metathesis reactions involving the formation of a variety of metal–element bonds through partner‐interchange of σ‐bond complexes. The key concept that defines a σ‐CAM process is a single transition state for metathesis that is connected by two intermediates that are σ‐bond complexes while the oxidation state of the metal remains constant in precursor, intermediates and product. This mechanism is appropriate in situations where σ‐bond complexes have been isolated or computed as well‐defined minima. Unlike several other mechanisms, it does not define the nature of the transition state. In this review, we highlight advances in the characterization and dynamic rearrangements of σ‐bond complexes, most notably alkane and zincane complexes, but also different geometries of silane and borane complexes. We set out a selection of catalytic and stoichiometric examples of the σ‐CAM mechanism that are supported by strong experimental and/or computational evidence. We then draw on these examples to demonstrate that the scope of the σ‐CAM mechanism has expanded to classes of reaction not envisaged in 2007 (additional σ‐bond ligands, agostic complexes, sp(2)‐carbon, surfaces). Finally, we provide a critical comparison to alternative mechanisms for metathesis of metal–element bonds.