Selective synthesis and electrochemical behavior of trans(Cl)- and cis(Cl)-[Ru(bpy)(CO)(2)Cl-2] complexes (bpy = 2,2'-bipyridine). Comparative studies of their electrocatalytic activity toward the reduction of carbon dioxide
Selective synthesis and electrochemical behavior of trans(Cl)- and cis(Cl)-[Ru(bpy)(CO)(2)Cl-2] complexes (bpy = 2,2'-bipyridine). Comparative studies of their electrocatalytic activity toward the reduction of carbon dioxide
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DOI：
10.1021/ic9701975
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发表时间：
1997-11-05
影响因子：
4.6
通讯作者：
Zsoldos, D
中科院分区：
文献类型：
--
作者：
ChardonNoblat, S;Deronzier, A;Zsoldos, D
选择性制备的合成程序（ca.描述了使用低聚[Ru（CO）（2）Cl-2]（n）前体的反式（Cl）-和顺式（Cl）-[Ru（bpy）（CO）（2）Cl-2]配合物1和2。该合成方法还提供了顺式（CO）-[Ru（bpy）（CO）（2）（C（O）OMe）Cl]配合物3的途径。与1相反，其给出强粘附的聚合物[Ru（bpy）（CO）（2）]（n）分子膜，2和3的电化学还原通过伴随氯配体损失的单电子还原过程形成二聚体5和6。配合物2、3、5和6作为高效的均相电催化剂用于在乙腈水溶液中选择性还原CO2为CO（95-97%法拉第产率）。
A synthetic procedure for the selective preparation (ca. 75% isolated yield) of trans(Cl)- and cis(Cl)-[Ru(bpy)(CO)(2)Cl-2] complexes 1 and 2, using an oligomeric [Ru(CO)(2)Cl-2](n) precursor, is described. The synthetic methodology also gives access to the cis(CO)-[Ru(bpy)(CO)(2)(C(O)OMe)Cl] complex 3. In contrast to 1, which gives strongly adherent polymeric [Ru(bpy)(CO)(2)](n) molecular films, electrochemical reduction of 2 and 3 forms dimers 5 and 6 by a one-electron reduction process accompanied by loss of a chloro ligand. Complexes 2, 3, 5, and 6 function as efficient homogeneous electrocatalysts for the selective reduction of CO2 to CO (95-97% faradaic yield) in aqueous acetonitrile.