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Article Dans Une Revue Angewandte Chemie International Edition Année : 2022

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

Résumé

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, sp2-carbon, surfaces). Finally, we provide a critical comparison to alternative mechanisms for metathesis of metal–element bonds.

Dates et versions

hal-03670324 , version 1 (17-05-2022)

Identifiants

Citer

Robin Perutz, Sylviane Sabo‐etienne, Andrew Weller. Metathesis by Partner Interchange in σ‐Bond Ligands: Expanding Applications of the σ‐CAM Mechanism. Angewandte Chemie International Edition, 2022, 61 (5), pp.e202111462. ⟨10.1002/anie.202111462⟩. ⟨hal-03670324⟩
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