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- Title
SiP Double Bonds: Experimental and Theoretical Study of an NHC-Stabilized Phosphasilenylidene.
- Authors
Geiß, Daniel; Arz, Marius I.; Straßmann, Martin; Schnakenburg, Gregor; Filippou, Alexander C.
- Abstract
An experimental and theoretical study of the first compound featuring a SiP bond to a two-coordinate silicon atom is reported. The NHC-stabilized phosphasilenylidene (IDipp)SiPMes* (IDipp=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene, Mes*=2,4,6- tBu3C6H2) was prepared by SiMe3Cl elimination from SiCl2(IDipp) and LiP(Mes*)SiMe3 and characterized by X-ray crystallography, NMR spectroscopy, cyclic voltammetry, and UV/Vis spectroscopy. It has a planar trans-bent geometry with a short SiP distance of 2.1188(7) Å and acute bonding angles at Si (96.90(6)°) and P (95.38(6)°). The bonding parameters indicate the presence of a SiP bond with a lone electron pair of high s-character at Si and P, in agreement with natural bond orbital (NBO) analysis. Comparative cyclic voltammetric and UV/Vis spectroscopic experiments of this compound, the disilicon(0) compound (IDipp)SiSi(IDipp), and the diphosphene Mes*PPMes* reveal, in combination with quantum chemical calculations, the isolobal relationship of the three double-bond systems.
- Subjects
CHEMICAL bonds; SILICON research; IMIDAZOLINES; CYCLIC voltammetry; NATURAL orbitals; QUANTUM chemistry
- Publication
Angewandte Chemie, 2015, Vol 127, Issue 9, p2777
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201411264