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.
A stable Ru(II)/Ru(III) mixed-valence state was observed in acetonitrile for the ruthenium binuclear complex bridged by dimercaptothiadiazolate (DeltaE(1/2) = 220 mV for Ru(2)(II,II)/Ru(2)(II,III) and Ru(2)(II,III)/Ru(2)(III,III) processes; K(com) = 5.3 x 10(3)). Upon protonation of the bridging ligand by the addition of equimolar p-toluenesulfonic acid, however, the mixed-valence state diminished (DeltaE(1/2) = 0 mV). The bridging ligand operates as a proton-induced switch of the electronic communication in the dimeric complex.
Tannai
Hidenori
H
Division of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810, Japan.
Tsuge
Kiyoshi
K
Sasaki
Yoichi
Y
D001952:Bridged-Ring Compounds / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004112:Dimercaprol / Q000737:chemistry; D004583:Electrons; D008024:Ligands; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000737:chemistry*; D011522:Protons; D012428:Ruthenium / Q000737:chemistry*; D013830:Thiadiazoles / Q000737:chemistry
D001952:Bridged-Ring Compounds; D008024:Ligands; D009942:Organometallic Compounds; D011522:Protons; D013830:Thiadiazoles; D004112:Dimercaprol; D012428:Ruthenium