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

journal contribution
posted on 2023-05-16, 13:31 authored by McGuinness, DS, Brian YatesBrian Yates, Cavell, KJ
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.

History

Publication title

Organometallics

Volume

21

Issue

24

Pagination

5408-5414

ISSN

0276-7333

Department/School

School of Natural Sciences

Publisher

American Chemical Society

Place of publication

Washington, DC, USA

Repository Status

  • Restricted

Socio-economic Objectives

Organic industrial chemicals (excl. resins, rubber and plastics)

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