Journal
CHEMISTRYSELECT
Volume 4, Issue 33, Pages 9696-9702Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/slct.201901821
Keywords
Oxido bridge; Ruthenium(III); Spectroscopic property; Sulfur donor ligand
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Funding
- JSPS KAKENHI [23510115, 25810052]
- Grants-in-Aid for Scientific Research [25810052, 23510115] Funding Source: KAKEN
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Novel diruthenium(III) complexes of general formula [Ru-2(III)(mu-O)(mu-CH3CO2)(2)(bpy)(2)L-2](PF6)(2) (L: tetrahydrothiophene, (3); 4,5-dihydro-3(2H)-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 angstrom, and the Ru-N(trans-to-oxido) length in 5 (2.157 A) 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: CH3CN), 5 and 6.
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