Switching of the Electronic Communication between Two {Ru(trpy)(bpy)} (trpy = 2,2‘:6‘,2‘ ‘-Terpyridine and bpy = 2,2‘-Bipyridine) Centers by Protonation on the Bridging Dimercaptothiadiazolato Ligand

• Published in: Inorganic chemistry Vol. 44; no. 15; pp. 5206 - 5208
• Main Authors: Tannai, Hidenori, Tsuge, Kiyoshi, Sasaki, Yoichi
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 25.07.2005
• Subjects: Bridged-Ring Compounds - chemistry; Crystallography, X-Ray; Dimercaprol - chemistry; Electrons; Ligands; Models, Molecular; Organometallic Compounds - chemistry; Protons; Ruthenium - chemistry; Thiadiazoles - chemistry
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic050672w

A stable Ru(II)/Ru(III) mixed-valence state was observed in acetonitrile for the ruthenium binuclear complex bridged by dimercaptothiadiazolate (ΔE 1/2 = 220 mV for Ru2(II,II)/Ru2(II,III) and Ru2(II,III)/Ru2(III,III) processes; K com = 5.3 × 103). Upon protonation of the bridging ligand by the addition of equimolar p-toluenesulfonic acid, however, the mixed-valence state diminished (ΔE 1/2 = 0 mV). The bridging ligand operates as a proton-induced switch of the electronic communication in the dimeric complex.