SiP Double Bonds: Experimental and Theoretical Study of an NHC‐Stabilized Phosphasilenylidene |
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| Authors: | Daniel Geiß Marius I. Arz Martin Straßmann Dr. Gregor Schnakenburg Prof. Dr. Alexander C. Filippou |
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| Affiliation: | Institut für Anorganische Chemie, Universit?t Bonn, Gerhard‐Domagk‐Strasse 1, 53121 Bonn (Germany) |
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| Abstract: | An experimental and theoretical study of the first compound featuring a Si?P bond to a two‐coordinate silicon atom is reported. The NHC‐stabilized phosphasilenylidene (IDipp)Si?PMes* (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 Si? P 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 Si?P 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)Si?Si(IDipp), and the diphosphene Mes*P?PMes* reveal, in combination with quantum chemical calculations, the isolobal relationship of the three double‐bond systems. |
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| Keywords: | isolobal relationship main‐group elements multiple bonds phosphorus silicon |
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