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  Carbene supported dimer of heavier ketenimine analogue with P and Si atoms.

Roy, S., Dittrich, B., Mondal, T., Koley, D., Stückl, A. C., Schwederski, B., et al. (2015). Carbene supported dimer of heavier ketenimine analogue with P and Si atoms. Journal of the American Chemical Society, 137(19), 6180-6183. doi:10.1021/jacs.5b03407.

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Item Permalink: http://hdl.handle.net/11858/00-001M-0000-0026-C867-4 Version Permalink: http://hdl.handle.net/11858/00-001M-0000-002A-51A8-3
Genre: Journal Article

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2151847.pdf (Publisher version), 480KB
 
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 Creators:
Roy, S., Author
Dittrich, B., Author
Mondal, T., Author
Koley, D., Author
Stückl, A. C., Author
Schwederski, B., Author
Kaim, W., Author
John, M., Author
Vasa, S. K.1, Author              
Linser, R.1, Author              
Roesky, H. W., Author
Affiliations:
1Research Group of Solid-State NMR-2, MPI for Biophysical Chemistry, Max Planck Society, ou_1950286              

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 Abstract: A cyclic alkyl(amino) carbene (cAAC) stabilized dimer [(cAAC)Si(P-Tip)]2 (2) (Tip = 2,4,6-triisopropylphenyl) is reported. 2 can be considered as a dimer of the heavier ketenimine (R2C=C=N-R) analogue. The dark-red rod-shaped crystals of 2 were synthesized by reduction of the precursor, cAAC-dichlorosilylene- stabilized phosphinidene (cAAC)SiCl2→P-Tip with sodium napthalenide. The crystals of 2 are storable at room temperature for several months, and stable up to 215 °C under an inert atmosphere. X-ray single-crystal diffraction revealed that 2 contains a cyclic non-planar four-membered SiPSiP ring. Magnetic susceptibility measurements confirmed the singlet spin ground state of 2. Cyclic voltammetry of 2 showed a quasi-reversible one-electron reduction indicating the formation of the corresponding radical anion 2•-, which was further characterized by EPR measurements in solution. The elec-tronic structure and bonding of 2 and 2•- were studied by theoretical calculations. The experimentally obtained data are in good agreement with the calculated values.

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Language(s): eng - English
 Dates: 2015-04-282015
 Publication Status: Published in print
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 Rev. Method: Peer
 Identifiers: DOI: 10.1021/jacs.5b03407
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Title: Journal of the American Chemical Society
Source Genre: Journal
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Pages: - Volume / Issue: 137 (19) Sequence Number: - Start / End Page: 6180 - 6183 Identifier: -