Issue 1, 2013

(NHCMe)SiCl4: a versatile carbene transfer reagent – synthesis from silicochloroform

Abstract

A new synthetic pathway for the N-heterocyclic carbene adduct (NHCMe)SiCl4 (2) (NHCMe = 1,3-dimethylimidazolidin-2-ylidene) using silicochloroform is presented. Supported by DFT calculations, the energy for dissociation of 2 into the carbene and the SiCl4 fragment was found to be comparable to carbene transfer reagents based on silver(I) chloride. Compound 2 was used to transfer the NHC ligand to three different phosphorus(III) chloro compounds, resulting in the neutral complexes (NHCMe)PCl3 (3a), (NHCMe)PCl2Ph (3b) and (NHCMe)PCl2Me (3c). The sterically non-demanding NHC ligand allowed the phosphorus(III) in complex 3a to be oxidized to phosphorus(V) without loss of the NHC ligand, and afford (NHCMe)PF4H (4). Furthermore, bis-carbene complexes of Ni(II) (5) and Pd(II) (6) were obtained by reacting 2 with the respective metal chlorides.

Graphical abstract: (NHCMe)SiCl4: a versatile carbene transfer reagent – synthesis from silicochloroform

Supplementary files

Article information

Article type
Edge Article
Submitted
08 Aug 2012
Accepted
13 Sep 2012
First published
14 Sep 2012

Chem. Sci., 2013,4, 77-83

(NHCMe)SiCl4: a versatile carbene transfer reagent – synthesis from silicochloroform

T. Böttcher, B. S. Bassil, L. Zhechkov, T. Heine and G. Röschenthaler, Chem. Sci., 2013, 4, 77 DOI: 10.1039/C2SC21214E

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