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)
%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 = {2019-07-15T13:41:23.000+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/b_schwederski},
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 = {2019-07-15T11:42:10.000+0200},
title = {Synthesis, Structure, and Electronic Properties of RuN6 Dinuclear Ru-Hbpp Complexes},
volume = 51,
year = 2012
}