(NHCMe)SiCl4: A versatile carbene transfer reagent-synthesis from silicochloroform

Tobias Böttcher; Bassem S. Bassil; Lyuben Zhechkov; Thomas Heine; Gerd Volker Röschenthaler

doi:10.1039/c2sc21214e

(NHC^Me)SiCl₄: A versatile carbene transfer reagent-synthesis from silicochloroform

Tobias Böttcher, Bassem S. Bassil, Lyuben Zhechkov, Thomas Heine, Gerd Volker Röschenthaler

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

47 Citations (Scopus)

Abstract

A new synthetic pathway for the N-heterocyclic carbene adduct (NHC ^Me)SiCl₄ (2) (NHC^Me = 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 (NHC^Me)PCl₃ (3a), (NHC^Me)PCl₂Ph (3b) and (NHC^Me)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 (NHC^Me)PF₄H (4). Furthermore, bis-carbene complexes of Ni(ii) (5) and Pd(ii) (6) were obtained by reacting 2 with the respective metal chlorides.

Original language	English
Pages (from-to)	77-83
Number of pages	7
Journal	Chemical Science
Volume	4
Issue number	1
DOIs	https://doi.org/10.1039/c2sc21214e
Publication status	Published - 2013

All Science Journal Classification (ASJC) codes

Chemistry(all)

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10.1039/c2sc21214e

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title = "(NHCMe)SiCl4: A versatile carbene transfer reagent-synthesis from silicochloroform",

abstract = "A new synthetic pathway for the N-heterocyclic carbene adduct (NHC Me)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.",

author = "Tobias B{\"o}ttcher and Bassil, {Bassem S.} and Lyuben Zhechkov and Thomas Heine and R{\"o}schenthaler, {Gerd Volker}",

year = "2013",

doi = "10.1039/c2sc21214e",

language = "English",

volume = "4",

pages = "77--83",

journal = "Chemical Science",

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publisher = "Royal Society of Chemistry",

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TY - JOUR

T1 - (NHCMe)SiCl4

T2 - A versatile carbene transfer reagent-synthesis from silicochloroform

AU - Böttcher, Tobias

AU - Bassil, Bassem S.

AU - Zhechkov, Lyuben

AU - Heine, Thomas

AU - Röschenthaler, Gerd Volker

PY - 2013

Y1 - 2013

N2 - A new synthetic pathway for the N-heterocyclic carbene adduct (NHC Me)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.

AB - A new synthetic pathway for the N-heterocyclic carbene adduct (NHC Me)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.

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U2 - 10.1039/c2sc21214e

DO - 10.1039/c2sc21214e

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JO - Chemical Science

JF - Chemical Science

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ER -

(NHC^Me)SiCl₄: A versatile carbene transfer reagent-synthesis from silicochloroform

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