%0 Journal Article %1 Sarkar.2004b %A Sarkar, Biprajit %A Kaim, Wolfgang %A Fiedler, Jan %A Duboc, Carole. %D 2004 %J Journal of the American Chemical Society %K UV arene areneruthenium azobispyridine bridged charge complex complex;redox complex;ruthenium dimer;EPR dimer;cyclic diruthenium iminomethylpyrazine mixed potential prepn spectra transfer transition valence voltammetry %N 45 %P 14706--14707 %R 10.1021/ja046397e %T Molecule-Bridged Mixed-Valent Intermediates Involving the RuI Oxidation State %V 126 %X Binuclear diruthenium cymene complexes bridged by azobis(pyridine) and pyrazine-bis-imine ligands are prepd. and studied by cyclic voltammetry. The diruthenium(II) complexes [(m-L)[RuCl(h6-MeC6H4iPr-4)]2](PF6)n, (1, L = 2,2'-azobispyridine (abpy), n = 1; 2, L = 2,5-bis(1-phenyliminoethyl)pyrazine (bpip), n = 2) were prepd. and characterized by NMR and EPR spectroscopy. Whereas the complex 1 has the structure of radical-anion-bridged RuIIRuII complex, the three-electron redn. under loss of both chloride ions produces the ions [(m-L)[Ru(Cym)]2]+, which could be identified as RuI(4d7)-contg. mixed-valent species (Ru0RuI or RuIRuII) by its intervalence charge-transfer bands around 1500 nm in UV-vis-NIR spectroelectrochem. and EPR, which shows rhombic g tensor anisotropy. The weak metal-metal interaction of the ds electrons from the eg set is responsible for the small electrochem. coupling with comproportionation consts. Kc $\approx$ 102. [on SciFinder(R)]

@article{Sarkar.2004b, abstract = {Binuclear diruthenium cymene complexes bridged by azobis(pyridine) and pyrazine-bis-imine ligands are prepd. and studied by cyclic voltammetry. The diruthenium(II) complexes [(\textgreek{m}-L)[RuCl(\textgreek{h}6-MeC6H4iPr-4)]2](PF6)n, (1, L = 2,2'-azobispyridine (abpy), n = 1; 2, L = 2,5-bis(1-phenyliminoethyl)pyrazine (bpip), n = 2) were prepd. and characterized by NMR and EPR spectroscopy. Whereas the complex 1 has the structure of radical-anion-bridged RuIIRuII complex, the three-electron redn. under loss of both chloride ions produces the ions [(\textgreek{m}-L)[Ru(Cym)]2]+, which could be identified as RuI(4d7)-contg. mixed-valent species (Ru0RuI or RuIRuII) by its intervalence charge-transfer bands around 1500 nm in UV-vis-NIR spectroelectrochem. and EPR, which shows rhombic g tensor anisotropy. The weak metal-metal interaction of the d\textgreek{s} electrons from the eg set is responsible for the small electrochem. coupling with comproportionation consts. Kc $\approx$ 102. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Sarkar, Biprajit and Kaim, Wolfgang and Fiedler, Jan and Duboc, Carole.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/29f99aa99299b5413b3d79ed4b99a3e16/huebleriac}, doi = {10.1021/ja046397e}, interhash = {61c9e4c8a6fd65f897db460b152b8ee1}, intrahash = {9f99aa99299b5413b3d79ed4b99a3e16}, issn = {0002-7863}, journal = {Journal of the American Chemical Society}, keywords = {UV arene areneruthenium azobispyridine bridged charge complex complex;redox complex;ruthenium dimer;EPR dimer;cyclic diruthenium iminomethylpyrazine mixed potential prepn spectra transfer transition valence voltammetry}, number = 45, pages = {14706--14707}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Molecule-Bridged Mixed-Valent Intermediates Involving the RuI Oxidation State}, volume = 126, year = 2004 }