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RuCl3·3H2O分别与6,6’-二甲基-2,2’-联吡啶(dmbp)和2,2’-联吡啶-6,6’-二甲醛(bpda)反应生成[cisRu(L)2Cl2]Cl·2H2O(L=dmbp,bpda),进一步用CF3SO3Ag脱氯得到[cis-Ru(L)2(H2O)2](CF3SO3)3.研究了4种配合物对1-己炔、苯乙炔和丙炔酸乙酯的催化环三聚作用,发现脱氯后的含水配合物催化活性有显著提高;体系中有水存在时,丙炔酸乙酯环三聚具有很强的区域选择性.催化机理研究表明,该催化过程为催化[2+2+2]环加成反应.钌杂环庚三烯或7-钌杂双环[2.2.1]-2,5-庚二烯是关键中间体,联吡啶配体上的6-甲酰基取代基水合后通过与丙炔酸乙酯的羰基形成分子内氢键影响环三聚产物的区域选择性.
RuCl3 · 3H2O reacted with 6,6’-dimethyl-2,2’-bipyridine (dmbp) and 2,2’-bipyridine-6,6’-dicarboxaldehyde (bpda) 2Cl2] Cl · 2H2O (L = dmbp, bpda) and further dechlorination with CF3SO3Ag gave [cis-Ru (L) 2 (H2O) 2] (CF3SO3) Acetylene and propiolactone catalyzed cyclometalation and found that the dechlorination of the aqueous complex catalytic activity was significantly improved; in the presence of water in the system, ethynyl ethyne ring cyclomethion has a strong regioselectivity The catalytic mechanism studies show that the catalytic process is a catalytic [2 + 2 + 2] cycloaddition reaction.Ruthenium heterocycloheptene or 7-rutheniumbicyclo [2.2.1] -2,5-heptadiene is the key The intermediate, the 6-formyl substituent on the bipyridine ligand, upon hydration, affects the regioselectivity of the cyclomerizabio product by intramolecular hydrogen bonding with the carbonyl group of ethyl propiolate.