Syntheses and structure of 8-, 7-, and 6-membered silacycloallenes
作者:Yi Pang、Scott A. Petrich、Victor G. Young、Mark S. Gordon、Thomas J. Barton
DOI:10.1021/ja00059a073
日期:1993.3
Encouraged by their recent success in the synthesis and structure determination of a tetrasilacyclohexyne, the authors have pursued the syntheses of strained silacycloallenes and report herein the first examples of isolable 6- and 7-membered rings containing 1,2-diene units. A key factor in their synthetic success was the finding that 1,3-bis(trimethylsilyl)-1-propyne is quantitatively converted to
pulsed laserphotolysis of 1,1,3,3-tetramethyl-2,2-diphenyl-1,2,3-trisilacycloheptane affords diphenylsilylene (SiPh2) with significantly higher selectivity than that reported previously from other SiPh2 precursors, allowing the direct detection of SiPh2 in solution for the first time. The UV/vis spectrum of the silylene in anhydrous hexane at 25 degrees C, determined by laser flash photolysis methods
Synthesis and structure of polysilabridged and doubly bridged allenes
作者:Toshio Shimizu、Fusao Hojo、Wataru Ando
DOI:10.1021/ja00061a009
日期:1993.4
Polysilacycloalka-1,2-dienes 1, 2, and 3 are synthesized by reactions of the Ph 2 C 3 dianion with corresponding dichloropolysilanes. X-ray crystallographic analyses of the tetrasilacyclohepta-1,2-diene 1 and the trisilacyclohexa-1,2-diene 3 show allenic sp carbons to be bent by 6 o and 19 o , respectively, and the torsional angles around the allenic moieties are 85.3 o and 52.2 o , respectively. Photoirradiation (254
聚硅杂环烷烃-1,2-二烯 1、2 和 3 是通过 Ph 2 C 3 二阴离子与相应的二氯聚硅烷反应合成的。四硅杂环庚基-1,2-二烯 1 和三硅杂环己-1,2-二烯 3 的 X 射线晶体学分析表明,丙二烯 sp 碳分别弯曲 6 o 和 19 o ,丙二烯部分周围的扭转角为分别为 85.3 o 和 52.2 o 。1 的光照射 (254 nm) 通过光诱导重排产生 1,3-桥连环丙烯 (11)。还报道了双桥联丙二烯八硅 [4.4]-丙二烯 4 之间的合成和 X 射线测定结构。在镁的存在下,二氯八甲基四硅烷与六氯丙烯反应合成间丙二烯4。
Electroreductive synthesis of oligosilanes and polysilanes with ordered sequences
achieved by the electroreductive cross-coupling reaction of chlorohydrosilanes with dichlorooligosilanes using magnesium electrodes. The electroreductive cross-coupling reaction of chlorodimethylsilane (1) with dichlorodiphenylsilane (2) or dichlorodiphenylgermane (4), for instance, gave 1,3-dihydro-1,1,3,3-tetramethyl-2,2-diphenyltrisilane (3) or bis(hydrodimethylsilyl)germane (5) in good yield. Compounds