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The σ‐CAM Mechanism: σ Complexes as the Basis of σ‐Bond Metathesis at Late‐Transition‐Metal Centers

2007; Wiley; Volume: 46; Issue: 15 Linguagem: Inglês

10.1002/anie.200603224

1521-3773

Robin N. Perutz, Sylviane Sabo‐Etienne,

Organometallic Complex Synthesis and Catalysis

Complexes in which a sigma-H--E bond (E=H, B, Si, C) acts as a two-electron donor to the metal center are called sigma complexes. Clues that it is possible to interconvert sigma ligands without a change in oxidation state derive from C--H activation reactions effecting isotope exchange and from dynamic rearrangements of sigma complexes (see Frontispiece). Through these pathways, metathesis of M--E bonds can occur at late transition metals. We call this process sigma-complex-assisted metathesis, or sigma-CAM, which is distinct from the familiar sigma-bond metathesis (typical for d(0) metals and requiring no intermediate) and from oxidative-reductive elimination mechanisms (inherently requiring intermediates with changed oxidation states and sometimes involving sigma complexes). There are examples of sigma-CAM mechanisms in catalysis, especially for alkane borylation and isotope exchange of alkanes. It may also occur in silylation and alkene hydrogenation.