%0 Journal Article %1 Kar.2007 %A Kar, Sanjib %A Sarkar, Biprajit %A Ghumaan, Sandeep %A Leboschka, Markus %A Fiedler, Jan %A Kaim, Wolfgang %A Lahiri, Goutam Kumar. %D 2007 %J Dalton Transactions %K bipyridine complex diazabutadiene dinuclear electrochem glyoxalbis hydroxyanil hydroxyphenyl prepn redox;ruthenium redox;spin ruthenium %N 19 %P 1934--1938 %R 10.1039/b617468j %T Ancillary ligand determination of the spin location in both oxidised and reduced forms of diruthenium complexes bridged by bis-bidentate 1,4-bis(2-phenolato)-1,4-diazabutadiene %X The rare bridging mode of 1,4-bis(2-hydroxyphenyl)-1,4-diazabutadiene = glyoxalbis(2-hydroxyanil) (L2-) is adopted in (μ-L2-)[RuII(bpy)2]22+ (12+), obtained as bis-perchlorate. Four well accessible redox forms of 1n (n = 4+, 3+, 2+, +) were characterized by UV-visible-NIR spectroelectrochem. The (3+) and (+) intermediates also were studied by EPR, both showing radical-type signals close to g = 2. This observation stands in Stark contrast to EPR results previously obtained for the related (μ-L)[Ru(acac)2]2n, n = + and -, both of which exhibit metal-centered spin. In combination with the UV-visible-NIR spectra these results suggest the preferential involvement of the multistep ligand redox system Ln- in the electron transfer processes. The relative stabilization of RuII by p-accepting bpy is made responsible for the oxidn. of the ligand L2- instead of the metal. [on SciFinder(R)]

@article{Kar.2007, abstract = {The rare bridging mode of 1,4-bis(2-hydroxyphenyl)-1,4-diazabutadiene = glyoxalbis(2-hydroxyanil) (L2-) is adopted in {(μ-L2-)[RuII(bpy)2]2}2+ (12+), obtained as bis-perchlorate. Four well accessible redox forms of 1n (n = 4+, 3+, 2+, +) were characterized by UV-visible-NIR spectroelectrochem. The (3+) and (+) intermediates also were studied by EPR, both showing radical-type signals close to g = 2. This observation stands in Stark contrast to EPR results previously obtained for the related {(μ-L)[Ru(acac)2]2}n, n = + and -, both of which exhibit metal-centered spin. In combination with the UV-visible-NIR spectra these results suggest the preferential involvement of the multistep ligand redox system Ln- in the electron transfer processes. The relative stabilization of RuII by \textgreek{p}-accepting bpy is made responsible for the oxidn. of the ligand L2- instead of the metal. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Kar, Sanjib and Sarkar, Biprajit and Ghumaan, Sandeep and Leboschka, Markus and Fiedler, Jan and Kaim, Wolfgang and Lahiri, Goutam Kumar.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2bc4b9da503200eb8c1fbd6b9cfdd0761/huebleriac}, doi = {10.1039/b617468j}, interhash = {641902e6e2a1c0db4b1f456e1c8d973f}, intrahash = {bc4b9da503200eb8c1fbd6b9cfdd0761}, issn = {1477-9226}, journal = {Dalton Transactions}, keywords = {bipyridine complex diazabutadiene dinuclear electrochem glyoxalbis hydroxyanil hydroxyphenyl prepn redox;ruthenium redox;spin ruthenium}, number = 19, pages = {1934--1938}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Ancillary ligand determination of the spin location in both oxidised and reduced forms of diruthenium complexes bridged by bis-bidentate 1,4-bis(2-phenolato)-1,4-diazabutadiene}, year = 2007 }