Addition of Methyl Grignard Reagents to Germasilenes and Digermenes: Unusual Ligand Exchange Reaction of the Resulting Germyl Grignard Reagents
作者:Craig E. Dixon、Matthew R. Netherton、Kim M. Baines
DOI:10.1021/ja981787k
日期:1998.10.1
tetramesityldigermene. The addition to the germasilene is regioselective, with the methyl group adding to the silicon end of the silicon−germanium double bond to produce a germylmagnesium iodide (or bromide) species. The germyl Grignardreagents give the corresponding germanes upon hydrolysis. At 110 °C in the presence of excess methylmagnesium halide, the mesityl substituents on the germyl Grignardreagent germanium
已发现甲基碘化镁(或溴化镁)可添加到四甲基苯并二甲基苯和四甲基苯二甲基苯中。添加到锗硅烯是区域选择性的,甲基添加到硅锗双键的硅端以产生锗基镁碘化物(或溴化物)物质。锗基格利雅试剂水解后产生相应的锗烷。在 110 °C 和过量的甲基卤化镁存在下,锗基格氏试剂锗原子上的甲基取代基被交换为甲基。已经提出了一种涉及 MesMgX 的 α-消除,然后将 MeMgX 添加到中间体锗烯的机制来解释观察到的配体交换。在 2,3-二甲基丁二烯的捕集实验中已经获得了中间体锗烯存在的证据。