Solvent mediated complete trans-to-cis isomerization of [Ru(polypyridine)(CO)2Cl2] complexes

被引：1
|
作者：
Oyama, Dai [1 ]
Kainuma, Shuya [1 ]
Akatsuka, Komi [1 ]
Abe, Ryosuke [1 ]
Takase, Tsugiko [1 ,2 ]
机构：
[1] Fukushima Univ, Cluster Sci & Engn, 1 Kanayagawa, Fukushima 9601296, Japan
[2] Fukushima Univ, Inst Environm Radioact, 1 Kanayagawa, Fukushima 9601296, Japan
来源：
JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2019年 / 900卷
关键词：
Ruthenium complexes; Carbonyl ligands; Polypyridines; Isomerization; Crystal structure; MOLECULAR-ORBITAL METHODS; RUTHENIUM COMPLEXES; CARBONYL-COMPLEXES; CO2; REDUCTION; MONONUCLEAR; BIPYRIDINE; LIGANDS; RU(BPY)(CO)(2)CL-2;
D O I：
10.1016/j.jorganchem.2019.120883
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
Trans(Cl)-[Ru(polypyridine)(CO)(2)Cl-2] complexes were completely isomerized to the corresponding cis(Cl)-isomers in the absence of a superacid or a reducing agent. X-ray crystallography was used to determine the molecular structures of the prepared cis-isomers. Spectroscopic, structural, and computational studies indicated that the isomerization occurs via an ethoxycarbonyl intermediate ({Ru-C(O)OC2H5}(+)), which is formed by the reaction of the solvent ethanol with a terminal carbonyl ligand. The electronic effects of the bidentate ligand in the complex were found to exert significant influence on isomerization. The mechanistic studies and the isomerization results will enable efficient syntheses of novel ruthenium complexes. (C) 2019 Elsevier B.V. All rights reserved.
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页数：6
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