silylated oniumions of group 15 elements I were synthesized by intramolecular cyclization of transient silylium ions II. Silylium ions II were prepared by the hydride transferreaction from silanes III using trityl cation as hydride acceptor. It was found that smaller ring systems could not be obtained by this approach. In these cases tritylphosphonium ions IV were isolated instead. Cations I and IV
通过瞬态硅离子II的分子内环化反应合成了第15组元素I的五元和六元环硅烷基化的鎓离子。通过使用三苯甲基阳离子作为氢化物受体的硅烷III的氢化物转移反应制备硅离子II。发现通过这种方法不能获得较小的环系统。在这些情况下,三苯甲基phosph离子IV被分离了。阳离子I和IV以四氟化五氟苯基硼酸盐的形式分离,并通过多核NMR光谱进行表征,在两种情况下通过X射线衍射分析进行表征。环鎓离子I显示出与等电子分子内的硼烷/膦受阻的路易斯对(FLP)相似的反应性。D05在M05-2X水平上的计算结果表明,新形成的Si–E键的强度是I [B(C 6 F 5)4 ]对分子氢惰性的主要原因。
Control of Si–C bond cleavage at carbon α to phosphorus. Suppression of facile protodesilylation of PPh<sub>2</sub>CH<sub>2</sub>SiMe<sub>2</sub>H by complexation through phosphorus to ruthenium and the X-ray crystal and molecular structure of [Ru(η<sup>6</sup>-p-cymene)Cl<sub>2</sub>(PPh<sub>2</sub>CH<sub>2</sub>SiMe<sub>2</sub>OH)]
作者:Ron D. Brost、Gregg C. Bruce、Stephen R. Stobart
DOI:10.1039/c39860001580
日期:——
Facile cleavage of the SiâC bond α to P in Ph2PCH2SiMe2H which is induced by HY (Y = OH, OMe, or Cl) is suppressed on complexation at Ru in [Ru(η6-cym)Cl2(PPh2CH2SiMe2H)](cym =p-cymene); instead the latter reacts where Y = OH to afford the silanol complex [Ru(η6-cym)Cl2(PPh2CH2SiMe2OH)] which has been structurally characterized by X-ray diffraction.
在 Ph2PCH2SiMe2H 中,HY(Y = OH、OMe 或 Cl)会诱导 SiâC 键 α 到 P 的快速裂解,而在 Ru 与 [Ru(δ-6-cym)Cl2(PPh2CH2SiMe2H)](cym =p-cymene)络合时,这种裂解会被抑制;相反,后者在 Y = OH 的情况下发生反应,生成硅醇复合物 [Ru(δ-6-ym)Cl2(PPh2CH2SiMe2OH)],该复合物已通过 X 射线衍射获得结构特征。
Brost, Ron D.; Bruce, Gregg C.; Grundy, Stephen L., Inorganic Chemistry, 1993, vol. 32, # 23, p. 5195 - 5200
作者:Brost, Ron D.、Bruce, Gregg C.、Grundy, Stephen L.、Stobart, Stephen R.
DOI:——
日期:——
HOLMES-SMITH, R. D.;OSEI, R. D.;STOBART, S. R., J. CHEM. SOC. PERKIN TRANS., 1983, N 4, 861-866
作者:HOLMES-SMITH, R. D.、OSEI, R. D.、STOBART, S. R.
DOI:——
日期:——
Holmes-Smith, Rupert D.; Osei, Rexford D.; Stobart, Stephen R., Journal of the Chemical Society. Perkin transactions I, 1983, p. 861 - 866
作者:Holmes-Smith, Rupert D.、Osei, Rexford D.、Stobart, Stephen R.