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SiP Double Bonds: Experimental and Theoretical Study of an NHC‐Stabilized Phosphasilenylidene
Author(s) -
Geiß Daniel,
Arz Marius I.,
Straßmann Martin,
Schnakenburg Gregor,
Filippou Alexander C.
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201411264
Subject(s) - natural bond orbital , lone pair , double bond , crystallography , chemistry , bond length , bent molecular geometry , cyclic voltammetry , spectroscopy , molecular geometry , computational chemistry , molecule , electrochemistry , crystal structure , density functional theory , organic chemistry , physics , electrode , quantum mechanics
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‐ t Bu 3 C 6 H 2 ) was prepared by SiMe 3 Cl elimination from SiCl 2 (IDipp) and LiP(Mes*)SiMe 3 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.