Issue 36, 2014

Synthesis and structural investigation of R2Si (R = Me, Ph) bridged di-N-heterocyclic carbenes

Abstract

Functionalization of the C4 carbon of an imidazol-derived N-heterocyclic carbene (NHC) may allow fine-tuning of the electronic and steric properties of the C2 carbene center. A facile route to silyl-functionalized di-N-heterocyclic carbenes (Di-NHCs) is described. Treatment of the polymeric lithiated NHC, {Li(IPrH)}n (1) (Li(IPrH) = {(N-2,6-iPr2C6H3)2CHCLi}C:) with a dichlorosilane affords monomeric silyl-functionalized Di-NHCs, R2Si(IPrH)2 (R = Ph, 2; Me, 3). Interestingly, silyl-functionalized mono-NHC, Ph2(Cl)Si(IPrH) (4) with a pendant chloro-substituent can also be exclusively isolated maintaining the reactants 1 and Ph2SiCl2 ratio. NHCs 2 and 4 readily form copper complexes, Ph2Si{(IPrH)CuCl}2 (5) and Ph2(Cl)Si{(IPrH)CuCl} (6), on reaction with CuCl. Straightforward conversion of an NHC to a Di-NHC (2 or 3) via C4 functionalization is reported for the first time. Molecular structures of 2, 4, 5 and 6 have been established by single crystal X-ray diffraction studies.

Graphical abstract: Synthesis and structural investigation of R2Si (R = Me, Ph) bridged di-N-heterocyclic carbenes

Supplementary files

Article information

Article type
Paper
Submitted
06 Jun 2014
Accepted
24 Jul 2014
First published
24 Jul 2014
This article is Open Access
Creative Commons BY license

Dalton Trans., 2014,43, 13704-13710

Synthesis and structural investigation of R2Si (R = Me, Ph) bridged di-N-heterocyclic carbenes

R. S. Ghadwal, S. O. Reichmann, E. Carl and R. Herbst-Irmer, Dalton Trans., 2014, 43, 13704 DOI: 10.1039/C4DT01681E

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