%0 Journal Article %1 Roeser.2012 %A Roeser, Stephan %A Ertem, Mehmed Z. %A Cady, Clyde %A Lomoth, Rainer %A Benet-Buchholz, Jordi %A Hammarstrom, Leif %A Sarkar, Biprajit %A Kaim, Wolfgang %A Cramer, Christopher J. %A Llobet, Antoni. %D 2012 %J Inorganic Chemistry %K acetonitrile atropisomerization complex complex;crystal complex;electronic complex;prepn deriv dinuclear mixed oxidn;cyclic pyridylpyrazole ruthenium spectra structure terpyridine valence;UV visible voltammetry %N 1 %P 320--327 %R 10.1021/ic201668r %T Synthesis, Structure, and Electronic Properties of RuN6 Dinuclear Ru-Hbpp Complexes %V 51 %X A series of RuN6 dinuclear Ru R1-Hbpp R2-trpy deriv. complexes (R1-Hbpp = 4-substituted 3,5-bis(2-pyridyl)pyrazole; R2-trpy = 4'-substituted terpyridine) of general formula RuII(R2-trpy)(MeCN)2(μ-R1-bpp)3+, (compds. 103+-143+; R1 = H, Me, or NO2, and R2 = H, Me, MeO) has been prepd. from their Cl- or AcO- bridged precursors. The complexes have been characterized by UV-visible, NMR, CV, and some by x-ray. Complexes 103+-143+, RuII-RuII, were oxidized by 1 equiv in soln., leading to the mixed valence RuII-RuIII complexes 104+-144+ contg. one unpaired electron and were characterized by EPR and UV-visible-near-IR, which showed metal-centered spin and the presence of low-energy IVCT bands. The Hab parameter indicates a relatively strong electronic coupling between the two ruthenium centers (class II). Further two electron oxidn. in soln. of the 103+-143+ gave EPR silent RuIII-RuIII complexes 105+-145+, that were further characterized by UV-visible-NIR. TD-DFT calcns. were employed to assign the nature of the UV-visible transitions for the complexes in the various oxidn. states, which are of metal to ligand charge transfer (MLCT) type for RuII-RuII and ligand to metal charge transfer (LMCT) type for RuIII-RuII and RuIII-RuIII. on SciFinder(R)

@article{Roeser.2012, abstract = {A series of RuN6 dinuclear Ru R1-Hbpp R2-trpy deriv. complexes (R1-Hbpp = 4-substituted 3,5-bis(2-pyridyl)pyrazole; R2-trpy = 4'-substituted terpyridine) of general formula {[RuII(R2-trpy)(MeCN)]2(μ-R1-bpp)}3+, (compds. 103+-143+; R1 = H, Me, or NO2, and R2 = H, Me, MeO) has been prepd. from their Cl- or AcO- bridged precursors. The complexes have been characterized by UV-visible, NMR, CV, and some by x-ray. Complexes 103+-143+, RuII-RuII, were oxidized by 1 equiv in soln., leading to the mixed valence RuII-RuIII complexes 104+-144+ contg. one unpaired electron and were characterized by EPR and UV-visible-near-IR, which showed metal-centered spin and the presence of low-energy IVCT bands. The Hab parameter indicates a relatively strong electronic coupling between the two ruthenium centers (class II). Further two electron oxidn. in soln. of the 103+-143+ gave EPR silent RuIII-RuIII complexes 105+-145+, that were further characterized by UV-visible-NIR. TD-DFT calcns. were employed to assign the nature of the UV-visible transitions for the complexes in the various oxidn. states, which are of metal to ligand charge transfer (MLCT) type for RuII-RuII and ligand to metal charge transfer (LMCT) type for RuIII-RuII and RuIII-RuIII. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Roeser, Stephan and Ertem, Mehmed Z. and Cady, Clyde and Lomoth, Rainer and Benet-Buchholz, Jordi and Hammarstrom, Leif and Sarkar, Biprajit and Kaim, Wolfgang and Cramer, Christopher J. and Llobet, Antoni.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2b4d14a3873de5809a3b3736b1c01772b/huebleriac}, doi = {10.1021/ic201668r}, interhash = {7f2d46b7e22b8674f6c788a2413a8783}, intrahash = {b4d14a3873de5809a3b3736b1c01772b}, issn = {0020-1669}, journal = {Inorganic Chemistry}, keywords = {acetonitrile atropisomerization complex complex;crystal complex;electronic complex;prepn deriv dinuclear mixed oxidn;cyclic pyridylpyrazole ruthenium spectra structure terpyridine valence;UV visible voltammetry}, number = 1, pages = {320--327}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Synthesis, Structure, and Electronic Properties of RuN6 Dinuclear Ru-Hbpp Complexes}, volume = 51, year = 2012 }