NHC -> SiCl4 : An Ambivalent Carbene-Transfer Reagent

Boettcher T, Steinhauer S, Lewis-Alleyne LC, Neumann B, Stammler H-G, Bassil BS, Roeschenthaler G-V, Hoge B (2015)
Chemistry - A European Journal 21(2): 893-899.

Journal Article | Published | English

No fulltext has been uploaded

Author
; ; ; ; ; ; ;
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)(2)SiCl3](+) 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 center dot OEt2, on the other hand, gave NHC -> BF3 as the product of NHC transfer. In addition, the highly Lewis acidic bis(pentafluoroethyl) silane (C2F5)(2)SiCl2 was treated with NHC -> SiCl4. In acetonitrile, the cationic silicon(IV) complexes [(NHC)SiCl3](+) and [(NHC)(2)SiCl3](+) were detected with [(C2F5)SiCl3](-) s counterion. A similar result was already reported for the reaction of NHC -> SiCl4 with (C2F5)(2)SiH2, which gave [(NHC)(2)SiCl2H][(C2F5)SiCl3]. If the reaction medium was changed to dichloromethane, the products of carbene transfer, NHC -> Si(C2F5)2Cl(2) and NHC -> Si(C2F5)(2)ClH, 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.
Publishing Year
ISSN
PUB-ID

Cite this

Boettcher T, Steinhauer S, Lewis-Alleyne LC, et al. NHC -> SiCl4 : An Ambivalent Carbene-Transfer Reagent. Chemistry - A European Journal. 2015;21(2):893-899.
Boettcher, T., Steinhauer, S., Lewis-Alleyne, L. C., Neumann, B., Stammler, H. - G., Bassil, B. S., Roeschenthaler, G. - V., et al. (2015). NHC -> SiCl4 : An Ambivalent Carbene-Transfer Reagent. Chemistry - A European Journal, 21(2), 893-899.
Boettcher, T., Steinhauer, S., Lewis-Alleyne, L. C., Neumann, B., Stammler, H. - G., Bassil, B. S., Roeschenthaler, G. - V., and Hoge, B. (2015). NHC -> SiCl4 : An Ambivalent Carbene-Transfer Reagent. Chemistry - A European Journal 21, 893-899.
Boettcher, T., et al., 2015. NHC -> SiCl4 : An Ambivalent Carbene-Transfer Reagent. Chemistry - A European Journal, 21(2), p 893-899.
T. Boettcher, et al., “NHC -> SiCl4 : An Ambivalent Carbene-Transfer Reagent”, Chemistry - A European Journal, vol. 21, 2015, pp. 893-899.
Boettcher, T., Steinhauer, S., Lewis-Alleyne, L.C., Neumann, B., Stammler, H.-G., Bassil, B.S., Roeschenthaler, G.-V., Hoge, B.: NHC -> SiCl4 : An Ambivalent Carbene-Transfer Reagent. Chemistry - A European Journal. 21, 893-899 (2015).
Boettcher, Tobias, Steinhauer, Simon, Lewis-Alleyne, Lesley C., Neumann, Beate, Stammler, Hans-Georg, Bassil, Bassem S., Roeschenthaler, Gerd-Volker, and Hoge, Berthold. “NHC -> SiCl4 : An Ambivalent Carbene-Transfer Reagent”. Chemistry - A European Journal 21.2 (2015): 893-899.
This data publication is cited in the following publications:
This publication cites the following data publications:

Export

0 Marked Publications

Open Data PUB

Web of Science

View record in Web of Science®

Sources

PMID: 25363673
PubMed | Europe PMC

Search this title in

Google Scholar