Carbene-Dichlorosilylene Stabilized Phosphinidenes Exhibiting Strong Intramolecular Charge Transfer Transition

2015 | journal article. A publication of Göttingen

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​Carbene-Dichlorosilylene Stabilized Phosphinidenes Exhibiting Strong Intramolecular Charge Transfer Transition​
Roy, S.; Stollberg, P.; Herbst-Irmer, R. ; Stalke, D. ; Andrada, D. M.; Frenking, G. & Roesky, H. W. ​ (2015) 
Journal of the American Chemical Society137(1) pp. 150​-153​.​ DOI: 

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Roy, Sudipta; Stollberg, Peter; Herbst-Irmer, Regine ; Stalke, Dietmar ; Andrada, Diego M.; Frenking, Gernot; Roesky, Herbert W. 
The unstable species dichlorosilylene was previously stabilized by carbene. The lone pair of electrons on the silicon atom of (carbene)SiCl2 can form a coordinate bond with metal-carbonyls. Herein we report that (carbene)SiCl2 can stabilize a phosphinidene (Ar-P, a carbone analogue) with the general formula carbene -> SiCl2 -> P-Ar (carbene = cyclic alkyl(amino) carbene (cAAC; 2) and N-heterocyclic carbene (NHC; 3)). Compounds 2 and 3 are stable, isolable, and storable at 0 degrees C (2) to room temperature (3) under an inert atmosphere. The crystals of 2 and 3 are dark blue and red, respectively. The intense blue color of 2 arises due to the strong intramolecular charge transfer (ICT) transition from pi(Si=P)->pi (cAAC). The electronic structure and bonding of 2, 3 were studied by theoretical calculations. The HOMO of the molecule is located on the pi(Si=P) bond, while the LUMO is located at the carbene moiety (cAAC or NHC). The dramatic change in color of these compounds from red (3, NHC) to blue (2, cAAC) is ascribed to the difference in energy of the LUMO within the carbenes (cAAC/NHC) due to a lower lying LUMO of cAAC.
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Journal of the American Chemical Society 
Deutsche Forschungsgemeinschaft [DFG RO 224/60-I]



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