2-单核和双核茂铁基-1,3-二烷基苯并咪唑盐的合成、结构及性质研究

Synthesis, Crystal Structure and Properties of Iodide and Hexafluorophosphate Salts of 2-Ferrocenyl (or Binuclear Ferrocenyl)-1,3-dialkylbenzimidazolium

以2-二茂铁基苯并咪唑(2)为原料,合成了1-甲基-2-二茂铁基-3-乙基苯并咪唑碘盐(4)和六氟磷酸盐(5);甲酰化的2,2-双二茂铁基丙烷(6)与邻苯二胺在甲醇作溶剂,回流,碘催化下反应,得到2-[1'-(2-二茂铁基丙烷-2-基)二茂铁-1-基]苯并咪唑(7),以7为原料合成了1-甲基-2-[1'-(2-二茂铁基丙烷-2-基)二茂铁-1-基]-3-乙基苯并咪唑碘盐(9)和六氟磷酸盐(10).电化学分析表明所得的盐化合物中,与苯并咪唑阳离子直接相连的二茂铁的氧化电位相对2和7均产生了较大正移.对化合物4的单晶结构进行了解析,晶体结构中存在π-π堆积.UV-Vis吸收光谱表明所得盐化合物具有光致电荷迁移现象.DSC-TG(差示扫描量热-热重)测试表明碘盐4对高氯酸铵(AP)热分解有较好催化效果.

Iodide salt 4 and hexafluorophosphate salt 5 of 1-methyl-2-ferrocenyl-3-ethylbenzimidazolium are prepared using 2-ferrocenylbenzimidazole 2 as starting material.2-[1＇-（2-Ferrocenylpropan-2-yl）ferrocen-1-yl]benzimidazole（7） is obtained by the reaction of formyl 2,2-diferrocenylpropane with o-diaminobenzene in the condition of methanol as solvent,reflux and catalysis of iodine.Iodide salt 9 and hexafluorophosphate salt 10 of 1-methyl-2-[1＇-（2-ferrocenylpropan-2-yl）-ferrocen-1yl]-3-ethylbenzimidazolium are synthesized using 7 as starting material.Oxidative potentials of ferrocenyl connected directly to benzimidazolium in these salts move to more positive position to a large extent.Crystal structure of 4 is explained and π-π stacking is showed.UV-Vis spectra shows that photoinduced charge transfer exists for salts.Iodide salt 4 presents good catalytic effect on decomposition of ammonium perchlorate（AP） in DSC-TG（differential scanning calorimetry-thermogravimetric） test.