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.; Kaim, W.; John, M.; Vasa, S. K.; Linser, R.; Roesky, H. W.

doi:10.1021/jacs.5b03407

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

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Vasa, S. K.
Research Group of Solid-State NMR-2, MPI for Biophysical Chemistry, Max Planck Society;

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Linser, R.
Research Group of Solid-State NMR-2, MPI for Biophysical Chemistry, Max Planck Society;

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http://pubs.acs.org/doi/pdf/10.1021/jacs.5b03407
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Citation

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.

Cite as: https://hdl.handle.net/11858/00-001M-0000-0026-C867-4

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.