%0 Journal Article %1 Ehret.2012 %A Ehret, Fabian %A Bubrin, Martina %A Huebner, Ralph %A Schweinfurth, David %A Hartenbach, Ingo %A Zalis, Stanislav %A Kaim, Wolfgang. %D 2012 %J Inorganic Chemistry %K acac benzoylphenyldiazene bipyridine;ruthenium crystal electronic prepn redox ruthenium spectroelectrochem structure thiobenzoylphenyldiazene %N 11 %P 6237--6244 %R 10.1021/ic300439h %T Filling Gaps in the Series of Noninnocent Hetero-1,3-diene Chelate Ligands: Ruthenium Complexes of Redox-Active a-Azocarbonyl and a-Azothiocarbonyl Ligands RNNC(R')E, E = O or S %V 51 %X 4-Center unsatd. chelate ligands A=B-C=D with redox activity to yield -A-B=C-D- in two steps were complemented by two new combinations RNNC(R')E, E = O or S, R = R' = Ph. The ligands N-benzoyl-N'-phenyldiazene = LO, and N-thiobenzoyl-N'-phenyldiazene = LS, (obtained in situ) form structurally characterized compds. [(acac)2Ru(L)] (1) with L = LO, and (3) with L = LS, and [(bpy)2Ru(L)](PF6), (2(PF6)) with L = LO, and (4(PF6)) with L = LS (acac- = 2,4-pentanedionato; bpy = 2,2'-bipyridine). According to spectroscopy and the N-N distances around 1.35 \AA and N-C bond lengths of $\sim$1.33 \AA, all complexes involve the monoanionic (radical) ligand form. For 1 and 3, the antiferromagnetic spin-spin coupling with electron transfer-generated RuIII leads to diamagnetic ground states of the neutral complexes, whereas the cations 2+ and 4+ are EPR-active radical ligand complexes of RuII. The complexes are reduced and oxidized in reversible 1-electron steps. EPR and UV-visible-NIR spectroelectrochem. in conjunction with time-dependent d. functional theory (TD-DFT) calcns. allowed the authors to assign the electronic transitions in the redox series, revealing mostly ligand-centered electron transfer: [(acac)2RuIII(L0)]+ .rdblhar. [(acac)2RuIII(L·-)] .rdblhar. [(acac)2RuIII(L2-)]-/[(acac)2RuII(L·-)]-, and [(bpy)2RuIII(L·-)]2+/[(bpy)2RuII(L0)]2+ .rdblhar. [(bpy)2RuII(L·-)]+ .rdblhar. [(bpy)2RuII(L2-)]0. The differences between the O and S contg. compds. are rather small in comparison to the effects of the ancillary ligands, acac- vs. bpy. [on SciFinder(R)]

@article{Ehret.2012, abstract = {4-Center unsatd. chelate ligands A=B-C=D with redox activity to yield -A-B=C-D- in two steps were complemented by two new combinations RNNC(R')E, E = O or S, R = R' = Ph. The ligands N-benzoyl-N'-phenyldiazene = LO, and N-thiobenzoyl-N'-phenyldiazene = LS, (obtained in situ) form structurally characterized compds. [(acac)2Ru(L)] (1) with L = LO, and (3) with L = LS, and [(bpy)2Ru(L)](PF6), (2(PF6)) with L = LO, and (4(PF6)) with L = LS (acac- = 2,4-pentanedionato; bpy = 2,2'-bipyridine). According to spectroscopy and the N-N distances around 1.35 {\AA} and N-C bond lengths of $\sim$1.33 {\AA}, all complexes involve the monoanionic (radical) ligand form. For 1 and 3, the antiferromagnetic spin-spin coupling with electron transfer-generated RuIII leads to diamagnetic ground states of the neutral complexes, whereas the cations 2+ and 4+ are EPR-active radical ligand complexes of RuII. The complexes are reduced and oxidized in reversible 1-electron steps. EPR and UV-visible-NIR spectroelectrochem. in conjunction with time-dependent d. functional theory (TD-DFT) calcns. allowed the authors to assign the electronic transitions in the redox series, revealing mostly ligand-centered electron transfer: [(acac)2RuIII(L0)]+ .rdblhar. [(acac)2RuIII(L·-)] .rdblhar. [(acac)2RuIII(L2-)]-/[(acac)2RuII(L·-)]-, and [(bpy)2RuIII(L·-)]2+/[(bpy)2RuII(L0)]2+ .rdblhar. [(bpy)2RuII(L·-)]+ .rdblhar. [(bpy)2RuII(L2-)]0. The differences between the O and S contg. compds. are rather small in comparison to the effects of the ancillary ligands, acac- vs. bpy. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Ehret, Fabian and Bubrin, Martina and Huebner, Ralph and Schweinfurth, David and Hartenbach, Ingo and Zalis, Stanislav and Kaim, Wolfgang.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/287e72dcc5eb743aa9a610d12cc74cc88/huebleriac}, doi = {10.1021/ic300439h}, interhash = {002c1f0d81f2502dd71258e0e81ee546}, intrahash = {87e72dcc5eb743aa9a610d12cc74cc88}, issn = {0020-1669}, journal = {Inorganic Chemistry}, keywords = {acac benzoylphenyldiazene bipyridine;ruthenium crystal electronic prepn redox ruthenium spectroelectrochem structure thiobenzoylphenyldiazene}, number = 11, pages = {6237--6244}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Filling Gaps in the Series of Noninnocent Hetero-1,3-diene Chelate Ligands: Ruthenium Complexes of Redox-Active \textgreek{a}-Azocarbonyl and \textgreek{a}-Azothiocarbonyl Ligands RNNC(R')E, E = O or S}, volume = 51, year = 2012 }