Synthesis and Application of New Conductive Compounds Bearing Ferrocene and S-Heterocycles.

(1)含二茂铁环的四硫富瓦烯(TTF)的合成；(2)含二茂铁环的噻吩齐聚物的合成。(1)以邻氨基苯甲酸为原料合成了2-二甲氧基膦-1，3-苯二硫醚，然后用Wittig-Horner方法在n-BuLi存在下与二茂铁酮(或苯基酮作对照)处理该膦酸酯，在-78℃至~0℃的干燥条件下得到了给体化合物。用这种方法合成了含甲基、苯基、杂环的二茂铁TTF的新型给体化合物。给电子体化合物在CH2Cl2中与已知的有机受体TCNQ或TCNQF4在回流温度下反应得到CT络合物。电导率测试表明，1，1‘-二取代二茂铁-TTFS-TCNQ化合物具有较高的电导率(σ=0.26 S cm~(-1)~(-1))。(2)用钯催化反应合成了以三键或双键键合在二茂铁环上的3-取代的噻吩衍生物。以钯为催化剂，研究了2-溴噻吩环与噻吩环的偶联反应。得到了低聚物化合物，但分离没有成功。对这些化合物的电化学性质也进行了测试。

Two themes were investigated, (1)synthesis of new donor compounds which have tetrathiafulvalenes (TTFs) bearing ferrocene ring derived to conducting charge transfer (CT) complex ; (2)synthesis of thiophene oligomers bearing ferrocene ring.(1): As an example, 2-dimethoxy-phosphinyl-1,3-benzodithiole was prepared from anthranilic acid, then treatment of this phosphonate ester with ferrocenyl ketones (or phenyl keton as comparison) using the Wittig-Horner method in the presence of n-BuLi at-78 to 〜0℃ in dry THE afforded the donor compounds. New donor compounds which have ferrocene-TTFs bearing methyl, phenyl, hetero ring were synthesized by this way. The CT complexes were obtained from the reaction of the donor compounds with the well-known organic acceptor TCNQ or TCNQF_4 in CH_2Cl_2 at reflux temperature. The electrical conductivity measurement showed a substantial conductivity (σ = 0.26 S cm^<-1> ) when the case of 1,1'-disubstituted Ferrocene-TTFs-TCNQ compound.(2)3-Substituted thiophene derivatives which bind to ferrocene ring by triple or double bond were synthesized using palladium catalytic reaction. The cuppling reaction of 2-bromothiophene and thiophane was carried out using palladium catalyst. Oligomer compounds were obtained, but separation were not succeeded. Electrochemical properties were also examined for these compounds.