Addition of stable nitroxide radical to stable divalent compounds of heavier group 14 elements
Addition of stable nitroxide radical to stable divalent compounds of heavier group 14 elements
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DOI：
10.1021/ja0356784
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发表时间：
2003-08-06
影响因子：
15
通讯作者：
Kira, M
中科院分区：
文献类型：
--
作者：
Iwamoto, T;Masuda, H;Kira, M
稳定的二烷基锗2和二烷基锡烯3分别与2，2，6，6-四甲基哌啶基-1-氧基(TEMPO)自由基(2当量)反应生成相应的1：2加合物4和5，其结构经核磁共振、质谱学和X-射线衍射法表征。两个TEMPO分子与Germylen2逐步加成的动力学表明，TEMPO对2的初始加成比第二个TEMPO加成得到的Germyl自由基慢1010倍。在定性摄动理论的基础上，讨论了速率差的来源。与2和3的反应不同，二烷基硅烯1与TEMPO反应生成了有趣的1，3-二恶二硅烷衍生物。
The reactions of stable cyclic dialkylgermylene2and dialkylstannylene3with 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO) radical (2 equiv) gave the corresponding 1:2 adducts4and5, respectively, which were characterized by NMR, MS, and X-ray analyses. The kinetics of the stepwise addition of two TEMPO molecules to germylene2revealed that the initial addition of TEMPO to2was 1010times slower than the second TEMPO addition to the resulting germyl radical. The origin of the rate difference was discussed on the basis of the qualitative perturbation theory. In contrast to the reactions of2and3, the reaction of dialkylsilylene1with TEMPO gave an interesting 1,3-dioxadisiletane derivative.