Donor-stabilized silyl cations. 5. Comparison between mono- and binuclear siliconium chelates

Inna Kalikhman; Vijeyakumar Kingston; Boris Gostevskii; Vadim Pestunovich; Dietmar Stalke; Bernhard Walfort; Daniel Kost

doi:10.1021/om020339p

Donor-stabilized silyl cations. 5. Comparison between mono- and binuclear siliconium chelates

Inna Kalikhman, Vijeyakumar Kingston, Boris Gostevskii, Vadim Pestunovich, Dietmar Stalke, Bernhard Walfort, Daniel Kost

Department of Chemistry

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

18 Scopus citations

Abstract

Binuclear hexacoordinate silicon chelates have been prepared and shown to have octahedral structure by X-ray crystallography. Their ionization in CD₂Cl₂ solution has been studied by ²⁹Si NMR spectroscopy. Only one Si-Cl bond in 5a-c ionizes at low temperature to form the monosiliconium bis-chelates 11a-c. Use of a more acidic solvent, CHFCl₂, facilitated the second ionization step to the disiliconium dichloride 12c. Replacement of the chloro ligands by better leaving groups (triflate, bromide, or iodide) caused complete ionization (7a-c, 8c, 9c) at room temperature. Crystal structure analyses of the binuclear siliconium triflates 7a,b show a square-pyramid geometry around the silicon atoms, with the ethylene bridge at the apex.

Original language	English
Pages (from-to)	4468-4474
Number of pages	7
Journal	Organometallics
Volume	21
Issue number	21
DOIs	https://doi.org/10.1021/om020339p
State	Published - 14 Oct 2002

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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abstract = "Binuclear hexacoordinate silicon chelates have been prepared and shown to have octahedral structure by X-ray crystallography. Their ionization in CD2Cl2 solution has been studied by 29Si NMR spectroscopy. Only one Si-Cl bond in 5a-c ionizes at low temperature to form the monosiliconium bis-chelates 11a-c. Use of a more acidic solvent, CHFCl2, facilitated the second ionization step to the disiliconium dichloride 12c. Replacement of the chloro ligands by better leaving groups (triflate, bromide, or iodide) caused complete ionization (7a-c, 8c, 9c) at room temperature. Crystal structure analyses of the binuclear siliconium triflates 7a,b show a square-pyramid geometry around the silicon atoms, with the ethylene bridge at the apex.",

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AU - Kalikhman, Inna

AU - Kingston, Vijeyakumar

AU - Gostevskii, Boris

AU - Pestunovich, Vadim

AU - Stalke, Dietmar

AU - Walfort, Bernhard

AU - Kost, Daniel

PY - 2002/10/14

Y1 - 2002/10/14

N2 - Binuclear hexacoordinate silicon chelates have been prepared and shown to have octahedral structure by X-ray crystallography. Their ionization in CD2Cl2 solution has been studied by 29Si NMR spectroscopy. Only one Si-Cl bond in 5a-c ionizes at low temperature to form the monosiliconium bis-chelates 11a-c. Use of a more acidic solvent, CHFCl2, facilitated the second ionization step to the disiliconium dichloride 12c. Replacement of the chloro ligands by better leaving groups (triflate, bromide, or iodide) caused complete ionization (7a-c, 8c, 9c) at room temperature. Crystal structure analyses of the binuclear siliconium triflates 7a,b show a square-pyramid geometry around the silicon atoms, with the ethylene bridge at the apex.

AB - Binuclear hexacoordinate silicon chelates have been prepared and shown to have octahedral structure by X-ray crystallography. Their ionization in CD2Cl2 solution has been studied by 29Si NMR spectroscopy. Only one Si-Cl bond in 5a-c ionizes at low temperature to form the monosiliconium bis-chelates 11a-c. Use of a more acidic solvent, CHFCl2, facilitated the second ionization step to the disiliconium dichloride 12c. Replacement of the chloro ligands by better leaving groups (triflate, bromide, or iodide) caused complete ionization (7a-c, 8c, 9c) at room temperature. Crystal structure analyses of the binuclear siliconium triflates 7a,b show a square-pyramid geometry around the silicon atoms, with the ethylene bridge at the apex.

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Donor-stabilized silyl cations. 5. Comparison between mono- and binuclear siliconium chelates

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