作者:René Kuzora、Axel Schulz、Alexander Villinger、Ronald Wustrack
DOI:10.1039/b911326f
日期:——
Starting from tris(trimethylsilyl)silane the novel 2-chloro-3,4-bis-tris(trimethylsilyl)silyl-cyclo-diphospha-diazenium-tetrachloridogallate salt (7) was prepared in a six step synthetic procedure including the synthesis of N-tris(trimethylsilyl)silyl-aminodichlorophosphine (4) and 1,3-dichloro-2,4-bis-tris(trimethylsilyl)silyl-cyclo-diphospha-diazane (5). All intermediate products along the reaction path have been isolated and fully characterized. The thermally stable cyclo-diphospha-diazenium-tetrachloridogallate (7) represents an interesting example of a binary cyclic P(III)/N four-membered heterocyclic cation, with a di- and tricoordinated P atom and a delocalized π bond along the NP(+)N unit. The structures of all compounds are discussed on the basis of experimental X-ray data. Moreover, for comparison the hitherto unknown 1-chloro-3-trifluoromethanesulfonato-2,4-bis-tris(trimethylsilyl)silyl-cyclo-diphosphadiazane (6) has been synthesized and fully characterized.
新型 2-氯-3,4-双-三(三甲基硅烷基)硅烷-环二磷杂-四氯棓酸盐 (7) 是以三(三甲基硅烷基)硅烷为起点,通过六步合成程序制备而成的,包括合成 N-三(三甲基硅烷基)硅烷-氨基二氯化膦 (4) 和 1.3-二氯-2,4-双-三(三甲基硅烷基)硅烷-环二磷杂-四氯棓酸盐 (5)、3-二氯-2,4-双-三(三甲基硅基)硅基-环二磷二氮杂环烷 (5)。反应路径上的所有中间产物都已分离出来并完全定性。热稳定的环二磷二氮四氯棓酸盐(7)是二元环状 P(III)/N 四元杂环阳离子的一个有趣例子,其中有一个二配位和三配位 P 原子,以及沿 NP(+)N 单元的一个脱位 π 键。根据 X 射线实验数据对所有化合物的结构进行了讨论。此外,为了比较迄今未知的 1-氯-3-三氟甲磺酰基-2,4-双-三(三甲基硅基)硅-环二膦二氮烷(6),我们还合成了该化合物,并对其进行了全面表征。