The sigma-CAM Mechanism: sigma complexes as the basis of sigma-bond metathesis at late-transition-metal centers |
| |
Authors: | Perutz Robin N Sabo-Etienne Sylviane |
| |
Institution: | Department of Chemistry, University of York, York, YO10 5DD, UK. rnp1@york.ac.uk |
| |
Abstract: | 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. |
| |
Keywords: | boranes dihydrogen complexes homogeneous catalysis hydride ligands silanes |
本文献已被 PubMed 等数据库收录! |
|