Isovalent and mixed-valent diruthenium complexes [(acac)2RuII (-bpytz)RuII(acac)2] and [(acac)2RuII(-bpytz)RuIII(acac)2](ClO4) (acac = acetylacetonate and bpytz = 3,6-bis(3,5-dimethylpyrazolyl)-1,2,4,5-tetrazine): synthesis, spectroelectrochemical, and epr investigation

Srikanta Patra; Biprajit Sarkar; Sandeep Ghumaan; Jan Fiedler; Wolfgang Kaim; Goutam Kumar Lahiri

doi:10.1021/ic049346r

Isovalent and mixed-valent diruthenium complexes [(acac)2RuII (-bpytz)RuII(acac)2] and [(acac)2RuII(-bpytz)RuIII(acac)2](ClO4) (acac = acetylacetonate and bpytz = 3,6-bis(3,5-dimethylpyrazolyl)-1,2,4,5-tetrazine): synthesis, spectroelectrochemical, and epr investigation

Inorg Chem. 2004 Sep 20;43(19):6108-13. doi: 10.1021/ic049346r.

Authors

Srikanta Patra¹, Biprajit Sarkar, Sandeep Ghumaan, Jan Fiedler, Wolfgang Kaim, Goutam Kumar Lahiri

Affiliation

¹ Department of Chemistry, Indian Institute of Technology-Bombay, Powai, Mumbai-400076, India.

PMID: 15360263
DOI: 10.1021/ic049346r

Abstract

The title compounds involving the structurally characterized bridging ligand bpytz were characterized, showing very strong electrochemical stabilization of the mixed-valent RuIIRuIII state (Kc = 10(13.9)) but no detectable (epsilon < 20 M(-1) cm(-1)) intervalence charge-transfer band in the infrared region. In situ reduction of the neutral precursor produces a diruthenium(II) complex of the bpytz radical anion according to EPR spectroscopy, whereas oxidation of the mixed-valent form leads to a diruthenium(III) species.