Reactions of alkali metal and yttrium alkyls with a sterically demanding bis(aryloxysilyl)methane: Formation of aryloxide complexes by Si-O bond cleavage
作者:Andrew D. Cornish、David P. Mills、William Lewis、Alexander J. Blake、Stephen T. Liddle
DOI:10.1016/j.crci.2010.01.017
日期:2010.6
with concomitant Si-C bond formation to give (BnSiMe2)2CH2 (5) as a colourless oil and the colourless, crystalline compounds [Y(OAr′)2(Bn)(THF)] (7), and [Y(OAr′)3(THF)2] (8) which were separated by fractional crystallisation. In an attempt to prepare 7 by a rational route, [Y(OAr′)2(I)(THF)2] (6) was prepared from the reaction of [Y(I)3(THF)3.5] with two equivalents of [K(OAr′)]. However, although 6 could
摘要 在辅助碱 NEt3 存在下,双(溴二甲基甲硅烷基)甲烷 (BrSiMe2)2CH2 (1) 与两当量的 2,6-二异丙基苯酚 (Ar'OH) 反应得到双(芳氧基甲硅烷基)甲烷 (Ar'OSiMe2)2CH2 (2) 后处理后呈无色油状物。在 [K(OBut)] 存在下,2 与 [Li(Bun)] 的反应促进了 Si-O 键的断裂,并且发现该反应的唯一可分离产物是无色结晶异双金属配合物 [Li(OAr) ′)}2K(OAr′)}2(THF)4] (3)。2 与一当量 [Li(Bun)] 在存在一当量 [K(OBut)] 的情况下进行原位反应,随后加入一当量 [Y(I)3(THF)3.5] 得到无色,晶体 [Y(OAr')(I)2(THF)3] (4) 作为唯一的可分离产物。在室温下,[Y(Bn)3(THF)3](Bn = CH2C6H5)和一当量的 2 在甲苯中没有观察到反应;加热溶液导致