About: Filling Gaps in the Series of Noninnocent Hetero-1,3-diene Chelate Ligands: Ruthenium Complexes of Redox-Active alpha-Azocarbonyl and alpha-Azothiocarbonyl Ligands RNNC(R ')E, E = O or S     Goto   Sponge   NotDistinct   Permalink

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  • The series of 4-center unsaturated chelate ligands A=B-C=D with redox activity to yield (-)A-B=C-D- in two steps has been complemented by two new combinations RNNC(R')E, E = O or S, R = R' = Ph. The ligands N-benzoyl-N'-phenyldiazene = L-O, and N-thiobenzoyl-N'-phenyldiazene = L-S, (obtained in situ) form structurally characterized compounds [(acac)(2)Ru(L)], 1 with L = L-O, and 3 with L = L-S, and [(bpy)(2)Ru(L)](PF6), 2(PF6) with L = L-O, and 4(PF6) with L = L-S (acac(-) = 2,4-pentanedionato; bpy = 2,2'-bipyridine). According to spectroscopy and the N-N distances around 1.35 angstrom and N-C bond lengths of about 1.33 angstrom, all complexes involve the monoanionic (radical) ligand form. For 1 and 3, the antiferromagnetic spin spin coupling with electron transfer-generated Rum leads to diamagnetic ground states of the neutral complexes, whereas the cations 2(+). and 4(+) are EPR-active radical ligand complexes of Ru-II. The complexes are reduced and oxidized in reversible one-electron steps. Electron paramagnetic resonance (EPR) and UV-vis-NIR spectroelectrochemistry in conjunction with time-dependent density functional theory (TD-DFT) calculations allowed us to assign the electronic transitions in the redox series, revealing mostly ligand-centered electron transfer: [(acac)(2)Ru-III(L-0)](+) reversible arrow [(acac)(2)Ru-III(L center dot-)] reversible arrow [(acac)(2)Ru-III(L2-)](-)/[(acac)(2)Ru-II(L center dot-)](-), and [(bpy)(2)Ru-III(L center dot-)](2+)/[(bpy)(2)Ru-II(L-0)](2+) reversible arrow [(bpy)(2)Ru-II(L center dot-)](+) reversible arrow [(bpy)(2)Ru-II(L2-)](0). The differences between the O and S containing compounds are rather small in comparison to the effects of the ancillary ligands, acac(-) versus bpy.
  • The series of 4-center unsaturated chelate ligands A=B-C=D with redox activity to yield (-)A-B=C-D- in two steps has been complemented by two new combinations RNNC(R')E, E = O or S, R = R' = Ph. The ligands N-benzoyl-N'-phenyldiazene = L-O, and N-thiobenzoyl-N'-phenyldiazene = L-S, (obtained in situ) form structurally characterized compounds [(acac)(2)Ru(L)], 1 with L = L-O, and 3 with L = L-S, and [(bpy)(2)Ru(L)](PF6), 2(PF6) with L = L-O, and 4(PF6) with L = L-S (acac(-) = 2,4-pentanedionato; bpy = 2,2'-bipyridine). According to spectroscopy and the N-N distances around 1.35 angstrom and N-C bond lengths of about 1.33 angstrom, all complexes involve the monoanionic (radical) ligand form. For 1 and 3, the antiferromagnetic spin spin coupling with electron transfer-generated Rum leads to diamagnetic ground states of the neutral complexes, whereas the cations 2(+). and 4(+) are EPR-active radical ligand complexes of Ru-II. The complexes are reduced and oxidized in reversible one-electron steps. Electron paramagnetic resonance (EPR) and UV-vis-NIR spectroelectrochemistry in conjunction with time-dependent density functional theory (TD-DFT) calculations allowed us to assign the electronic transitions in the redox series, revealing mostly ligand-centered electron transfer: [(acac)(2)Ru-III(L-0)](+) reversible arrow [(acac)(2)Ru-III(L center dot-)] reversible arrow [(acac)(2)Ru-III(L2-)](-)/[(acac)(2)Ru-II(L center dot-)](-), and [(bpy)(2)Ru-III(L center dot-)](2+)/[(bpy)(2)Ru-II(L-0)](2+) reversible arrow [(bpy)(2)Ru-II(L center dot-)](+) reversible arrow [(bpy)(2)Ru-II(L2-)](0). The differences between the O and S containing compounds are rather small in comparison to the effects of the ancillary ligands, acac(-) versus bpy. (en)
Title
  • Filling Gaps in the Series of Noninnocent Hetero-1,3-diene Chelate Ligands: Ruthenium Complexes of Redox-Active alpha-Azocarbonyl and alpha-Azothiocarbonyl Ligands RNNC(R ')E, E = O or S
  • Filling Gaps in the Series of Noninnocent Hetero-1,3-diene Chelate Ligands: Ruthenium Complexes of Redox-Active alpha-Azocarbonyl and alpha-Azothiocarbonyl Ligands RNNC(R ')E, E = O or S (en)
skos:prefLabel
  • Filling Gaps in the Series of Noninnocent Hetero-1,3-diene Chelate Ligands: Ruthenium Complexes of Redox-Active alpha-Azocarbonyl and alpha-Azothiocarbonyl Ligands RNNC(R ')E, E = O or S
  • Filling Gaps in the Series of Noninnocent Hetero-1,3-diene Chelate Ligands: Ruthenium Complexes of Redox-Active alpha-Azocarbonyl and alpha-Azothiocarbonyl Ligands RNNC(R ')E, E = O or S (en)
skos:notation
  • RIV/61388955:_____/12:00384814!RIV13-AV0-61388955
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  • I, P(LD11086)
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  • 11
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  • 136456
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  • RIV/61388955:_____/12:00384814
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  • TRANSITION-METAL-COMPLEXES; DENSITY-FUNCTIONAL CALCULATIONS; ORDER REGULAR APPROXIMATION (en)
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  • US - Spojené státy americké
http://linked.open...ontrolniKodProRIV
  • [96E11A21F85B]
http://linked.open...i/riv/nazevZdroje
  • Inorganic Chemistry
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  • 51
http://linked.open...iv/tvurceVysledku
  • Hartenbach, I.
  • Kaim, W.
  • Záliš, Stanislav
  • Schweinfurth, D.
  • Hübner, R.
  • Bubrin, M.
  • Ehret, F.
http://linked.open...ain/vavai/riv/wos
  • 000304728500030
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  • 0020-1669
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  • 10.1021/ic300439h
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