State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, 5625 Renmin Street, Changchun 130022, Jilin, China.
J Org Chem. 2011 Aug 5;76(15):6067-74. doi: 10.1021/jo2006768. Epub 2011 Jul 1.
Singly bonded PhCH(2)C(60)-C(60)CH(2)Ph dimers are generated via controlled-potential bulk electroreduction and electrooxidation of 1,2-(PhCH(2))HC(60). The reaction mixture was purified by HPLC, and the isolated fraction was characterized with single-crystal X-ray diffractions, (1)H and (13)NMR, MS, elemental analysis, and cyclic voltammetry. It was shown that the fraction consists of two HPLC-inseparable PhCH(2)C(60)-C(60)CH(2)Ph regioisomers, which are assigned as the meso and racemic regioisomers. The bulk electrolysis processes for the formation of the dimers were followed by in situ cyclic voltammetry and were further corroborated with an in situ voltammetric titration of 1,2-(PhCH(2))HC(60) with tetra-n-butylammonium hydroxide (TBAOH), on the basis of which a reaction mechanism is proposed.
通过对 1,2-(PhCH(2))HC(60)的控制电位 bulk electroreduction 和 electrooxidation，生成了单键合的 PhCH(2)C(60)-C(60)CH(2)Ph 二聚体。反应混合物通过 HPLC 进行纯化，并用单晶 X 射线衍射、(1)H 和 (13)NMR、MS、元素分析和循环伏安法对分离出的部分进行了表征。结果表明，该部分由两种 HPLC 不可分离的 PhCH(2)C(60)-C(60)CH(2)Ph 区域异构体组成，它们被指定为间位和外消旋区域异构体。通过原位循环伏安法跟踪二聚体形成的 bulk electrolysis 过程，并进一步通过用四丁基氢氧化铵 (TBAOH) 对 1,2-(PhCH(2))HC(60)进行原位伏安滴定来证实，基于此提出了反应机制。
