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同价和混合价态的二钌配合物[(acac)2RuII (-bpytz)RuII(acac)2]和[(acac)2RuII(-bpytz)RuIII(acac)2](ClO4)（acac = 乙酰丙酮，bpytz = 3,6-双(3,5-二甲基吡唑基)-1,2,4,5-四嗪）：合成、光谱电化学及电子顺磁共振研究

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 .

作者信息

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

机构信息

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

出版信息

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

DOI:10.1021/ic049346r
PMID:15360263
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.

摘要

对涉及结构已表征的桥连配体bpytz的标题化合物进行了表征，结果表明混合价态RuIIRuIII态具有很强的电化学稳定性（Kc = 10(13.9)），但在红外区域未检测到可察觉的（ε < 20 M(-1) cm(-1)）价间电荷转移带。根据电子顺磁共振光谱，中性前体的原位还原产生了bpytz自由基阴离子的二钌(II)配合物，而混合价态形式的氧化则导致了二钌(III)物种。

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