%0 Journal Article %1 Mondal.2013 %A Mondal, Prasenjit %A Ehret, Fabian %A Bubrin, Martina %A Das, Amit %A Mobin, Shaikh M. %A Kaim, Wolfgang %A Lahiri, Goutam Kumar. %D 2013 %J Inorganic Chemistry %K DFT calcn complex complex;dinuclear crystal dinuclear electrochem indigodiphenylimine pentanedionato prepn ruthenium structure %N 15 %P 8467--8475 %R 10.1021/ic400390b %T A Diruthenium Complex of a \dqNindigo\dq Ligand %V 52 %X (μ-Nindigo)Ru(acac)22 (1), H2(Nindigo) = indigo-N,N'-diphenylimine and acac- = 2,4-pentanedionate, was structurally characterized in the rac form, which exhibits two edge-sharing six-membered chelate rings involving ruthenium, and the former b-diketiminato functions with a twist angle of 33.9° around the central C-C bond. The metric parameters suggest a neutral p acceptor bridge contg. coupled s-trans configurated a-diimines, which are coordinated by two ruthenium(II) centers. DFT calcns. confirm the exptl. structure and oxidn. state assignment of the rac form; both diastereoisomers are present in soln. according to 1H NMR spectroscopy. A very intense long-wavelength MLCT absorption at 630 nm (e = 66,800 M-1 cm-1) and a weaker near-IR band at 1120 nm (e = 3000 M-1 cm-1) are obsd. for the CH3CN soln. Reversible 1-electron redn. and oxidn. steps were studied by cyclic voltammetry, differential pulse voltammetry, EPR, and UV-visible-NIR spectroelectrochem. to exhibit metal-centered oxidn. and mixed metal/ligand-centered redn. These results are supported by TD-DFT calcns. of the species rac- or meso-1n, n = 3+, 2+, +, 0, -, 2-. on SciFinder(R)

@article{Mondal.2013, abstract = {{(μ-Nindigo)[Ru(acac)2]2} (1), H2(Nindigo) = indigo-N,N'-diphenylimine and acac- = 2,4-pentanedionate, was structurally characterized in the rac form, which exhibits two edge-sharing six-membered chelate rings involving ruthenium, and the former \textgreek{b}-diketiminato functions with a twist angle of 33.9° around the central C-C bond. The metric parameters suggest a neutral \textgreek{p} acceptor bridge contg. coupled s-trans configurated \textgreek{a}-diimines, which are coordinated by two ruthenium(II) centers. DFT calcns. confirm the exptl. structure and oxidn. state assignment of the rac form; both diastereoisomers are present in soln. according to 1H NMR spectroscopy. A very intense long-wavelength MLCT absorption at 630 nm (\textgreek{e} = 66,800 M-1 cm-1) and a weaker near-IR band at 1120 nm (\textgreek{e} = 3000 M-1 cm-1) are obsd. for the CH3CN soln. Reversible 1-electron redn. and oxidn. steps were studied by cyclic voltammetry, differential pulse voltammetry, EPR, and UV-visible-NIR spectroelectrochem. to exhibit metal-centered oxidn. and mixed metal/ligand-centered redn. These results are supported by TD-DFT calcns. of the species rac- or meso-1n, n = 3+, 2+, +, 0, -, 2-. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Mondal, Prasenjit and Ehret, Fabian and Bubrin, Martina and Das, Amit and Mobin, Shaikh M. and Kaim, Wolfgang and Lahiri, Goutam Kumar.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/27ee3f089225f37c969230bdbd913a5ac/huebleriac}, doi = {10.1021/ic400390b}, interhash = {72f3833a886261819859be6fcfeb908e}, intrahash = {7ee3f089225f37c969230bdbd913a5ac}, issn = {0020-1669}, journal = {Inorganic Chemistry}, keywords = {DFT calcn complex complex;dinuclear crystal dinuclear electrochem indigodiphenylimine pentanedionato prepn ruthenium structure}, number = 15, pages = {8467--8475}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {A Diruthenium Complex of a {\dq}Nindigo{\dq} Ligand}, volume = 52, year = 2013 }