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- Title
NHC→SiCl<sub>4</sub>: An Ambivalent Carbene-Transfer Reagent.
- Authors
Böttcher, Tobias; Steinhauer, Simon; Lewis‐Alleyne, Lesley C.; Neumann, Beate; Stammler, Hans‐Georg; Bassil, Bassem S.; Röschenthaler, Gerd‐Volker; Hoge, Berthold
- Abstract
The addition of BCl3 to the carbene-transfer reagent NHC→SiCl4 (NHC=1,3-dimethylimidazolidin-2-ylidene) gave the tetra- and pentacoordinate trichlorosilicon(IV) cations [(NHC)SiCl3]+ and [(NHC)2SiCl3]+ with tetrachloroborate as counterion. This is in contrast to previous reactions, in which NHC→SiCl4 served as a transfer reagent for the NHC ligand. The addition of BF3 ⋅OEt2, on the other hand, gave NHC→BF3 as the product of NHC transfer. In addition, the highly Lewis acidic bis(pentafluoroethyl)silane (C2F5)2SiCl2 was treated with NHC→SiCl4. In acetonitrile, the cationic silicon(IV) complexes [(NHC)SiCl3]+ and [(NHC)2SiCl3]+ were detected with [(C2F5)SiCl3]− as counterion. A similar result was already reported for the reaction of NHC→SiCl4 with (C2F5)2SiH2, which gave [(NHC)2SiCl2H][(C2F5)SiCl3]. If the reaction medium was changed to dichloromethane, the products of carbene transfer, NHC→Si(C2F5)2Cl2 and NHC→Si(C2F5)2ClH, respectively, were obtained instead. The formation of the latter species is a result of chloride/hydride metathesis. These compounds may serve as valuable precursors for electron-poor silylenes. Furthermore, the reactivity of NHC→SiCl4 towards phosphines is discussed. The carbene complex NHC→PCl3 shows similar reactivity to NHC→SiCl4, and may even serve as a carbene-transfer reagent as well.
- Subjects
CARBENES; CATIONS; ACETONITRILE; DICHLOROMETHANE; PHOSPHINE
- Publication
Chemistry - A European Journal, 2015, Vol 21, Issue 2, p893
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201404628