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Contents Vol 64(8)

Novel Intramolecular CAryl–S Bond Activation by an Electron Rich, Ring-Expanded-NHC-Rh centre: A Combined Experimental and DFT Study

Abeer Binobaid A , Kingsley J. Cavell A C , Mikhail S. Nechaev B C and Benson M. Kariuki A
+ Author Affiliations
- Author Affiliations

A School of Chemistry, Main Building, Cardiff University, Cardiff CF10 3AT, Wales, UK.

B Department of Chemistry, M.V. Lomonosov Moscow State University, Leninskie Gory 1/3 and A.V. Topchiev Institute of Petrochemical Synthesis, RAS, Leninsky Prosp., 29, Moscow, 119991, Russian Federation.

C Corresponding authors. Email: cavellkj@cf.ac.uk; nechaev@nmr.chem.msu.ru

Australian Journal of Chemistry 64(8) 1141-1147 https://doi.org/10.1071/CH11243
Submitted: 15 June 2011  Accepted: 1 July 2011   Published: 19 August 2011

Abstract

The reaction of (o-MeSPh)-N-functionalized tetrahydropyrimidinium salts with KN(SiMe3)2 and [Rh(COD)Cl]2 in THF leads to the formation of a novel dimeric RhIII bis-carbene complex. The reaction involves the unexpected cleavage/oxidative addition of the aryl-sulfur bond to give dimeric metallated RhIII with bridging MeS< moieties. This unusual reaction is probably a consequence of the sterically imposing structure and strong donor capacity of ring-expanded N-heterocyclic carbenes (RE-NHCs). An X-ray structure of the [(Ph,DIPP-NHC)Rh(Cl)(SMe)2] product complex has been obtained, and DFT studies were undertaken to gain an insight into the reaction pathway.


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