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- Title
Dichlorosilylene Transfer to a P-Fluorophosphaalkene: The Route to a C-Dichlorofluorosilyl-Functionalized Dialkyldiphosphene.
- Authors
Mitrofan, Cristina; Gust, Thorsten; Zanin, Andreas; Bîrzoi, Roxana M.; Jones, Peter G.; du Mont, Wolf‐W.; Hayashi, Satoko; Nakanishi, Waro; Marsmann, Heinrich C.
- Abstract
Reactions of the (trichlorosilyl)germane Me3GeSiCl3 and of the unsymmetric disilane Me3GeSiCl3 with the P-fluorophosphaalkene (Me3Si)2C=PF (1) proceed with transfer of SiCl2 (2) leading to the new C-dichlorofluorosilyl-functionalized dialkyldiphosphene (Cl2FSi)(Me3Si)2CP=PC(SiCl2F)(SiMe3)2 (6), which was characterized by X-ray crystallography. The P-phosphanylphosphaalkene (Me3Si)2C=PP[C(SiCl2F)(SiMe3)2]SiCl2F (8a) was detected in the reaction mixtures by 31P NMR spectroscopy, accompanied by its isomer 8b, presumably (Cl2FSi)(Me3Si)C=PP[C(SiCl2F)(SiMe3)2]SiMe3. The unsymmetric dimers 8a and 8b rearrange by a 1,3-(P→C) silyl group shift, providing the inversion-symmetric diphosphene 6. Compound 6 was transformed with selenium into a selenadiphosphirane (9). Quantum chemical calculations were performed on intermediates on the route from 1 and 2 to the metastable unsymmetric dimers 8a and 8b. The addition of SiCl2 to the P=C bond of 1, followed by ring opening of the silaphosphirane 4, provides the phosphinidene (Me3Si)2(Cl2FSi)CP (5), which rearranges further to isomeric P-silylphosphaalkenes (Me3Si)2C=PSiCl2F (7a) and (Cl2FSi)(Me3Si)C=PSiMe3 (7b). Rapid phosphinidene-phosphaalkene P-P coupling reactions of 5 with 7a and with 7b followed by 1,2-(P→P) silyl group shift of ylide-type dimers 11a and 11b explain the formation of the observed species 8a and 8b. The absence of species related to 8b in previous experiments on the reactions of the P-chlorophosphaalkene (Me3Si)2C=PCl (1') with Si2Cl6, with Me3GeSiCl3, and with Me3- SiSiCl3, allows us to suggest that in the P-chlorophosphaalkene case nucleophile-supported SiCl2 insertion into the P-Cl bond or the substitutive Cl-/SiCl3 - exchange are the preferred routes to the metastable P-(trichlorosilyl)phosphaalkene (Me3Si)2C= PSiCl3.
- Subjects
FLUORINE compounds; SILYLENES; ALKENES; PHOSPHENES; X-ray crystallography; CHLORIDES
- Publication
European Journal of Inorganic Chemistry, 2017, Vol 2017, Issue 11, p1526
- ISSN
1434-1948
- Publication type
Article
- DOI
10.1002/ejic.201601411