Reactions of dialkyl(trimethylsilyl)phosphanes RRЈPSiMe 3 (1:compounds R 3 SnSiCl 3 (19a-c) that decompose providing (R 3 Sn) 2 Si(SiCl 3 ) 2 (18a-c) and nBu 3 SnSi(SiCl 3 ) 3 (20c). R, RЈ = tBu; 3: R, RЈ = iPr; 5: R = iPr, RЈ = tBu) with Si 2 Cl 6 provide stable trichlorosilylphosphanes RRЈPSiCl 3 (2, 4, 6);Subsequently, compounds 19a-c decompose providing increasing amounts of 18a-c. Stannylphosphane 17b is also the reactions of silyl-and stannylamines of iPr 2 NMMe 3 (M = Si: 11; M = Sn: 12) with Si 2 Cl 6 , however, provide the stable cleaved by SiCl 4 leading to 6 with liberation of Et 3 SnCl, whereas 17b is formed from the reaction of 5 with Et 3 SnCl pentachlorodisilanylamine iPr 2 NSi 2 Cl 5 (13). Heating of 1 with the technical mixture Me 2 (Cl)SiSiCl 2 Me/(MeCl 2 Si) 2 under liberation of Me 3 SiCl. The suggestion of an extra stabilisation of P-Si bonds of trichlorosilylphosphanes was yields the stable silylphosphane tBu 2 PSiMe 2 Cl (8) and the disilanylphosphane tBu 2 PSi(Me)(Cl)Si(Me)Cl 2 (9). Methsubjected to direct evidence through the structure determination of the trichlorosilylphosphane tBu 2 PSiCl 3 (2) ylation of 9 with MeLi gave tBu 2 PSi 2 Me 5 10, which was isolated in a pure state. Reactions of tBu(iPr)PSiMe 3 (5) and in the gas phase by electron diffraction. This crowded molecule has a "normal" P-Si bond length of 225.0(12) pm; of organometal phosphanes tBu(iPr)PMR 3 (14: M = Ge, R = Me; 17a-c: M = Sn; R = Me, Et, nBu) with Si 2 Cl 6 were its C 1 symmetric conformation with both tBu groups and the SiCl 3 group twisted about 17°from the perfectly staggered monitored by 31 P, 29 Si, and 119 Sn NMR. -In the first step of these reactions, new tBu(iPr)PSi 2 Cl 5 (7) is formed. 7 is positions, and with each of the three groups tilted about 6°a way from each other, allows to reduce steric strain. accompanied by increasing amounts of tBu(iPr)PSiCl 3 (6) and Me 3 GeSiCl 3 (15)/(Me 3 Ge) 2 Si(SiCl 3 ) 2 (16) or traces of products of reductive C-trichlorosilylations, [3,4] we recently
The gas-phase molecular structures of chloropyrazine, 2-, 3-and 4-chloropyridine have been determined by ab initio calculations and by gas-phase electron diffraction (GED) supplemented with rotation constants and restraints based on ab initio calculations. Geometries are compared to those of their respective parent compounds and other related systems to demonstrate the effects of chlorination on ring geometry.
Reactions of dialkyl(trimethylsilyl)phosphanes RR′PSiMe3 (1:R, R′ = tBu; 3: R, R′ = iPr; 5: R = iPr, R′ = tBu) with Si2Cl6 provide stable trichlorosilylphosphanes RR′PSiCl3 (2, 4, 6); the reactions of silyl‐ and stannylamines of iPr2NMMe3 (M = Si: 11; M = Sn: 12) with Si2Cl6, however, provide the stable pentachlorodisilanylamine iPr2NSi2Cl5 (13). Heating of 1 with the technical mixture Me2(Cl)SiSiCl2Me/(MeCl2Si)2 yields the stable silylphosphane tBu2PSiMe2Cl (8) and the disilanylphosphane tBu2PSi(Me)(Cl)Si(Me)Cl2 (9). Methylation of 9 with MeLi gave tBu2PSi2Me510, which was isolated in a pure state. Reactions of tBu(iPr)PSiMe3 (5) and of organometal phosphanes tBu(iPr)PMR3 (14: M = Ge, R = Me; 17a–c: M = Sn; R = Me, Et, nBu) with Si2Cl6 were monitored by 31P, 29Si, and 119Sn NMR. – In the first step of these reactions, new tBu(iPr)PSi2Cl5 (7) is formed. 7 is accompanied by increasing amounts of tBu(iPr)PSiCl3 (6) and Me3GeSiCl3 (15)/(Me3Ge)2Si(SiCl3)2 (16) or traces of compounds R3SnSiCl3 (19a–c) that decompose providing (R3Sn)2Si(SiCl3)2 (18a–c) and nBu3SnSi(SiCl3)3 (20c). Subsequently, compounds 19a–c decompose providing increasing amounts of 18a–c. Stannylphosphane 17bis also cleaved by SiCl4 leading to 6 with liberation of Et3SnCl, whereas 17bis formedfrom the reaction of 5 with Et3SnCl under liberation of Me3SiCl. The suggestion of an extra stabilisation of P–Si bonds of trichlorosilylphosphanes was subjected to direct evidence through the structure determination of the trichlorosilylphosphane tBu2PSiCl3 (2) in the gas phase by electron diffraction. This crowded molecule has a “normal” P–Si bond length of 225.0(12) pm; its C1 symmetric conformation with both tBu groups and the SiCl3 group twisted about 17° from the perfectly staggered positions, and with each of the three groups tilted about 6° away from each other, allows to reduce steric strain.
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