%0 Journal Article %1 Kar.2005b %A Kar, Sanjib %A Sarkar, Biprajit %A Ghumaan, Sandeep %A Roy, Dipankar %A Urbanos, Francisco A. %A Fiedler, Jan %A Sunoj, Raghavan B. %A Jimenez-Aparicio, Reyes %A Kaim, Wolfgang %A Lahiri, Goutam Kumar. %D 2005 %J Inorganic Chemistry %K ESR bisbidentate bridging complex electrochem gloxabishydroxyanil property redox ruthenium %N 24 %P 8715--8722 %R 10.1021/ic050950r %T A New Coordination Mode of the Photometric Reagent Glyoxalbis(2-hydroxyanil) (H2gbha): Bis-Bidentate Bridging by gbha2- in the Redox Series (μ-gbha)Ru(acac)22n (n = -2, -1, 0, +1, +2), Including a Radical-Bridged Diruthenium(III) and a RuIII/RuIV Intermediate %V 44 %X The bis-bidentate bridging function of gbha2- with N,O-/N,O- coordination was obsd. for the 1st time in the complex (m-gbha)RuIII(acac)22 (1). D. functional theory calcns. of 1 yield a triplet ground state with a large (DE \textgreater 6000 cm-1) singlet-triplet gap. Intermol. antiferromagnetic coupling was obsd. (J $\approx$ -5.3 cm-1) for the solid. Complex 1 undergoes two 1-electron redn. and two 1-electron oxidn. steps; the five redox forms (μ-gbha)Ru(acac)22n (n = -2, -1, 0, +1, +2) were characterized by UV-visible-NIR spectroelectrochem. (NIR = near IR). The paramagnetic intermediates were also studied by EPR spectroscopy. The monoanion with a comproportionation const. Kc of 2.7 $\times$ 108 does not exhibit an NIR band for a RuIII/RuII mixed-valent situation; it is best described as a 1,4-diazabutadiene radical anion contg. ligand gbha.bul.3-, which binds two ruthenium(III) centers. A RuIII-type EPR spectrum with g1 = 2.27, g2 = 2.21, and g3 = 1.73 is obsd. as a result of antiferromagnetic coupling between one RuIII and the ligand radical. The EPR-active monocation (Kc = 1.7 $\times$ 106) exhibits a broad (Dn1/2 = 2600 cm-1) intervalence charge-transfer band at 1800 nm, indicating a valence-averaged (Ru3·5)2 formulation (class III) with a tendency toward class II (borderline situation). on SciFinder(R)

@article{Kar.2005b, abstract = {The bis-bidentate bridging function of gbha2- with N,O-/N,O- coordination was obsd. for the 1st time in the complex (\textgreek{m}-gbha)[RuIII(acac)2]2 (1). D. functional theory calcns. of 1 yield a triplet ground state with a large (\textgreek{D}E {\textgreater} 6000 cm-1) singlet-triplet gap. Intermol. antiferromagnetic coupling was obsd. (J $\approx$ -5.3 cm-1) for the solid. Complex 1 undergoes two 1-electron redn. and two 1-electron oxidn. steps; the five redox forms {(μ-gbha)[Ru(acac)2]2}n (n = -2, -1, 0, +1, +2) were characterized by UV-visible-NIR spectroelectrochem. (NIR = near IR). The paramagnetic intermediates were also studied by EPR spectroscopy. The monoanion with a comproportionation const. Kc of 2.7 $\times$ 108 does not exhibit an NIR band for a RuIII/RuII mixed-valent situation; it is best described as a 1,4-diazabutadiene radical anion contg. ligand gbha.bul.3-, which binds two ruthenium(III) centers. A RuIII-type EPR spectrum with g1 = 2.27, g2 = 2.21, and g3 = 1.73 is obsd. as a result of antiferromagnetic coupling between one RuIII and the ligand radical. The EPR-active monocation (Kc = 1.7 $\times$ 106) exhibits a broad (\textgreek{Dn}1/2 = 2600 cm-1) intervalence charge-transfer band at 1800 nm, indicating a valence-averaged (Ru3·5)2 formulation (class III) with a tendency toward class II (borderline situation). [on SciFinder(R)]}, added-at = {2018-08-09T10:59:25.000+0200}, author = {Kar, Sanjib and Sarkar, Biprajit and Ghumaan, Sandeep and Roy, Dipankar and Urbanos, Francisco A. and Fiedler, Jan and Sunoj, Raghavan B. and Jimenez-Aparicio, Reyes and Kaim, Wolfgang and Lahiri, Goutam Kumar.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/24bb0d988bd0856b73c2f55b661313495/galaktoze}, doi = {10.1021/ic050950r}, interhash = {4e1b7bc9f7a94478cf81a5df5f9875e0}, intrahash = {4bb0d988bd0856b73c2f55b661313495}, issn = {0020-1669}, journal = {Inorganic Chemistry}, keywords = {ESR bisbidentate bridging complex electrochem gloxabishydroxyanil property redox ruthenium}, number = 24, pages = {8715--8722}, timestamp = {2018-08-09T13:02:07.000+0200}, title = {A New Coordination Mode of the Photometric Reagent Glyoxalbis(2-hydroxyanil) (H2gbha): Bis-Bidentate Bridging by gbha2- in the Redox Series {(μ-gbha)[Ru(acac)2]2}n (n = -2, -1, 0, +1, +2), Including a Radical-Bridged Diruthenium(III) and a RuIII/RuIV Intermediate}, volume = 44, year = 2005 }