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The First Bis( μ ‐acetato)( μ ‐oxido)diruthenium(III) Complexes Containing Sulfur Donor Ligands
Author(s) -
Ido Yohei,
Fujihara Takashi,
Sugaya Tomoaki,
Nagasawa Akira
Publication year - 2019
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201901821
Subject(s) - tetrahydrothiophene , chemistry , ligand (biochemistry) , pyridine , sulfur , thiazole , redox , density functional theory , stereochemistry , medicinal chemistry , nitrogen , crystallography , inorganic chemistry , computational chemistry , organic chemistry , biochemistry , receptor
Novel diruthenium(III) complexes of general formula [Ru III 2 ( μ ‐O)‐( μ ‐CH 3 CO 2 ) 2 (bpy) 2 L 2 ](PF 6 ) 2 (L: tetrahydrothiophene, ( 3 ); 4,5‐dihydro‐3(2 H )‐thiophenone, ( 4 ); thiazole, ( 5 ); 4‐methylthiazole, ( 6 ); bpy: 2,2’‐bipyridine), which contain sulfur or nitrogen donor ligands at the trans ‐to‐oxido sites, have been synthesized. The Ru–S bond distance in 4 is determined by X‐ray crystallography to be 2.447 Å, and the Ru–N( trans ‐to‐oxido) length in 5 (2.157 Å) is similar to that of the complex having pyridine as the L ligand, 1 . The spectroscopic properties and redox behavior of the complexes bearing sulfur donor ligands have been investigated and compared with those containing nitrogen donor ligands. The potentials of the redox couples of Ru 2 II,III /Ru 2 III,III and Ru 2 III,III /Ru 2 III,IV for 3 and 4 shift to positive regions compared with those of complexes with nitrogen donor ligands, 1 , 5 and 6 . The density functional theory (DFT) calculations reveal that the contribution of the trans ligand to the visible absorption is larger in 3 and 4 than in 1 , 2 (L: CH 3 CN), 5 and 6 .