Synthesis, properties, and reactions of a stable carbanion derived from alkynyldihydrofullerene: 1-Octynyl-C-60 carbanion

被引:78
作者
Murata, Y
Motoyama, K
Komatsu, K
Wan, TSM
机构
[1] KYOTO UNIV,INST CHEM RES,UJI,KYOTO 611,JAPAN
[2] HONG KONG UNIV SCI & TECHNOL,DEPT CHEM,KOWLOON,HONG KONG
关键词
D O I
10.1016/0040-4020(96)00115-9
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Stable 1-octynyl-C-60 carbanion (2(-)) was generated by the reaction of 1-octynyl-C-60-H with t-BuOK in THF, and its structure was confirmed by H-1 and C-13 NMR spectra. The redox properties were studied by cyclic voltammetry, and were shown to involve a one electron oxidation process affording a dimer of the corresponding radical, in addition to stepwise reduction processes. In accord with the results of semiempirical MO calculations (AM1), the reaction of anion 2(-) with various carbon electrophiles afforded the 1,2- or 1,4-disubstituted dihydrofullerenes. The reaction site was apparently controlled by electron density of anion 2(-) and the steric effects. (C) 1996 Elsevier Science Ltd
引用
收藏
页码:5077 / 5090
页数:14
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