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Department of Chemistry, Inorganic Chemistry Section, Jadavpur University, Kolkata-700 032, India E-mail : samaresh_b@hotmail.com Acetone thiosemicarbazone (abbreviated as Hactsc) reacts with [Ru(trpy)Cl3] in refluxing ethanol in the presence of triethylamine to afford [Ru(trpy)(actsc)(SCN)] as a purple solid. The thiocyanate ion is generated in situ via a ruthenium mediated C-N bond cleavage of acetone thiosemicarbazone. Crystal structure of [Ru(trpy)(actsc)(SCN)] has been determined, which shows that actsc is coordinated to the metal center as a mono-anionic bidentate NS-donor, along with a terpyridine and a N-bound thiocyanate. The complex is diamagnetic, and shows characteristic 1H NMR signals and electronic transitions in the visible region. Cyclic voltammetry on [Ru(trpy)(actsc)(SCN)] shows an irreversible oxidation at 1.13 V vs SCE and an irreversible reduction at –1.24 V vs SCE. DFT calculation has been carried out to explain the electronic spectral, as well as electrochemical, observations. The [Ru(trpy)(actsc)(SCN)] complex is found to efficiently catalyze transfer-hydrogenation reaction. |
