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Theoretical study of methyl-Pd-II N-heterocyclic silylene and germylene complexes: Comparisons to N-heterocyclic carbene reactivity

Citation

McGuinness, DS and Yates, BF and Cavell, KJ, Theoretical study of methyl-Pd-II N-heterocyclic silylene and germylene complexes: Comparisons to N-heterocyclic carbene reactivity, Organometallics, 21, (24) pp. 5408-5414. ISSN 0276-7333 (2002) [Refereed Article]

DOI: doi:10.1021/om020750c

Abstract

A theoretical study of methyl-Pd heterocyclic silylene and germylene complexes has been carried out and reveals a very low activation barrier for methyl migration to the silylene or germylene ligand, but indicates that, in the absence of solvent or counterion effects, reductive elimination of silicenium or germacenium cations is less likely. The results have been compared with those for the more common N-heterocyclic carbenes, and the activation barrier for coupling of the methyl group with C/Si/Ge was found to follow the order Si < Ge < C. The effect of solvent on the reaction has been modeled by incorporation of THF into the calculations on the silylene, which lowers the energy of all stationary points on the potential energy surface. Furthermore, with THF present reductive elimination of the silicenium cation becomes feasible. The results are discussed in terms of the implications they have on the potential application of these ligands in homogeneous catalysis.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Theoretical and Computational Chemistry
Research Field:Quantum Chemistry
Objective Division:Manufacturing
Objective Group:Industrial Chemicals and Related Products
Objective Field:Organic Industrial Chemicals (excl. Resins, Rubber and Plastics)
Author:McGuinness, DS (Dr David McGuinness)
Author:Yates, BF (Professor Brian Yates)
ID Code:24305
Year Published:2002
Web of Science® Times Cited:25
Deposited By:Chemistry
Deposited On:2002-08-01
Last Modified:2011-08-02
Downloads:0

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