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

被引:58
作者
Patra, S
Sarkar, B
Ghumaan, S
Fiedler, J
Kaim, W [1 ]
Lahiri, GK
机构
[1] Indian Inst Technol, Dept Chem, Bombay 400076, Maharashtra, India
[2] Univ Stuttgart, Inst Anorgan Chem, D-70550 Stuttgart, Germany
[3] Acad Sci Czech Republ, J Heyrovsky Inst Phys Chem, CZ-18223 Prague, Czech Republic
关键词
D O I
10.1021/ic049346r
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The title compounds involving the structurally characterized bridging ligand bpytz were characterized, showing very strong electrochemical stabilization of the mixed-valent (RuRuIII)-Ru-II state (K-c = 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.
引用
收藏
页码:6108 / 6113
页数:6
相关论文
共 55 条
[1]   From organotransition-metal chemistry toward molecular electronics: Electronic communication between ligand-bridged metals [J].
Astruc, D .
ACCOUNTS OF CHEMICAL RESEARCH, 1997, 30 (09) :383-391
[2]   CHEMISTRY OF THE [RU(RQ)(TAP)2]Z FAMILY - AUTHENTIC CATECHOLATES, REDUCTION POTENTIALS, AND SPECTRA (RQ = QUINONE SEMIQUINONE CATECHOLATE - TAP = 2-(M-TOLYLAZO)PYRIDINE - Z = O, +/-, +/-2) [J].
BAG, N ;
PRAMANIK, A ;
LAHIRI, GK ;
CHAKRAVORTY, A .
INORGANIC CHEMISTRY, 1992, 31 (01) :40-45
[3]   Optical transitions of symmetrical mixed-valence systems in the Class II-III transition regime [J].
Brunschwig, BS ;
Creutz, C ;
Sutin, N .
CHEMICAL SOCIETY REVIEWS, 2002, 31 (03) :168-184
[4]   Energy surfaces, reorganization energies, and coupling elements in electron transfer [J].
Brunschwig, BS ;
Sutin, N .
COORDINATION CHEMISTRY REVIEWS, 1999, 187 :233-254
[5]   CHARGE-TRANSFER AND INTRALIGAND ELECTRONIC SPECTRA OF BIPYRIDYL COMPLEXES OF IRON, RUTHENIUM, AND OSMIUM .2. TERVALENT COMPLEXES [J].
BRYANT, GM ;
FERGUSSO.JE .
AUSTRALIAN JOURNAL OF CHEMISTRY, 1971, 24 (02) :275-&
[6]   Dinuclear bis(bipyridine)ruthenium(II) complexes [(bpy)2 RuII{L}2-RuII(bpy)2]2+ incorporating thiouracil-based dianionic asymmetric bridging ligands:: synthesis, structure, redox and spectroelectrochemical properties [J].
Chakraborty, S ;
Laye, RH ;
Munshi, P ;
Paul, RL ;
Ward, MD ;
Lahiri, GK .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 2002, (11) :2348-2353
[7]   A dinuclear bis(bipyridine)ruthenium(II) complex, [(bpy)2RuII{L2-}RuII(bpy)2]2+, incorporating an unusual non-innocent bridging ligand containing a p-benzoquinonediimine fragment:: synthesis, structure, redox, and UV/VIS/NIR and EPR spectroelectrochemical properties [J].
Chakraborty, S ;
Laye, RH ;
Paul, RL ;
Gonnade, RG ;
Puranik, VG ;
Ward, MD ;
Lahiri, GK .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 2002, (06) :1172-1179
[8]   Synthesis and mixed valence aspects of [{(L)ClRu}2(μ-tppz)]n+ incorporating 2, 2′-dipyridylamine (L) as ancillary and 2,3,5,6-tetrakis(2-pyridyl)pyrazine (tppz) as bridging ligand [J].
Chanda, N ;
Sarkar, C ;
Fiedler, J ;
Kaim, W ;
Lahiri, GK .
DALTON TRANSACTIONS, 2003, (18) :3550-3555
[9]   Dinuclear ruthenium(II) complexes [{(L)ClRuII}2(μ-tppz)]2+ (L = an arylazopyridine ligand) incorporating tetrakis(2-pyridyl) pyrazine (tppz) bridging ligand:: synthesis, structure and spectroelectrochemical properties [J].
Chanda, N ;
Laye, RH ;
Chakraborty, S ;
Paul, RL ;
Jeffrey, JC ;
Ward, MD ;
Lahiri, GK .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 2002, (18) :3496-3504
[10]   Synthesis and properties of [Ru2(acac)4(bptz)]n+ (n=0, 1) and crystal structure of [Ru2(acac)4(bptz)] [J].
Chellamma, S ;
Lieberman, M .
INORGANIC CHEMISTRY, 2001, 40 (13) :3177-3180