%0 Journal Article %1 Mondal.2014d %A Mondal, Prasenjit %A Agarwala, Hemlata %A Jana, Rahul Dev %A Plebst, Sebastian %A Grupp, Anita %A Ehret, Fabian %A Mobin, Shaikh M. %A Kaim, Wolfgang %A Lahiri, Goutam Kumar. %D 2014 %J Inorganic Chemistry %K DFT EPR acetylacetonato bisphenyliminoacenaphthene calcn complex complex;ruthenium crystal electrochem prepn ruthenium structure tetrakispyridylpyrazine %N 14 %P 7389--7403 %R 10.1021/ic500730m %T Sensitivity of a Strained C-C Single Bond to Charge Transfer: Redox Activity in Mononuclear and Dinuclear Ruthenium Complexes of Bis(arylimino)acenaphthene (BIAN) Ligands %V 53 %X Ru(acac)2(BIAN), BIAN = bis(arylimino)acenaphthene (aryl = Ph (1a), 4-MeC6H4 (2a), 4-OMeC6H4 (3a), 4-ClC6H4 (4a), 4-NO2C6H4 (5a)), were synthesized and structurally, electrochem., spectroscopically, and computationally characterized. The a-diimine sections of the compds. exhibit intrachelate ring bond lengths 1.304 \AA \textless d(CN) \textless 1.334 and 1.425 \AA \textless d(CC) \textless 1.449 \AA, which indicate considerable metal-to-ligand charge transfer in the ground state, approaching a RuIII(BIAN.bul.-) oxidn. state formulation. The particular structural sensitivity of the strained peri-connecting C-C bond in the BIAN ligands toward metal-to-ligand charge transfer is discussed. Oxidn. of Ru(acac)2(BIAN) produces EPR and UV-visible-NIR (NIR = near IR) spectroelectrochem. detectable RuIII species, while the redn. yields predominantly BIAN-based spin, in agreement with d. functional theory (DFT) spin-d. calcns. Variation of the substituents from CH3 to NO2 has little effect on the spin distribution but affects the absorption spectra. Dinuclear (μ-tppz)Ru(Cl)(BIAN)2(ClO4)2, tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine; aryl (BIAN) = Ph (1b(ClO4)2), 4-MeC6H4 (2b(ClO4)2), 4-OMeC6H4 (3b(ClO4)2), 4-ClC6H4 (4b(ClO4)2), were also obtained and investigated. The structure detn. of 2b(ClO4)2 and 3b(ClO4)2 reveals trans configuration of the chloride ligands and unreduced BIAN ligands. The DFT and spectroelectrochem. results (UV-visible-NIR, EPR) indicate oxidn. to a weakly coupled RuIIIRuII mixed-valent species but redn. to a tppz-centered radical state. The effect of the p electron-accepting BIAN ancillary ligands is to diminish the metal-metal interaction due to competition with the acceptor bridge tppz. on SciFinder(R)

@article{Mondal.2014d, abstract = {[Ru(acac)2(BIAN)], BIAN = bis(arylimino)acenaphthene (aryl = Ph (1a), 4-MeC6H4 (2a), 4-OMeC6H4 (3a), 4-ClC6H4 (4a), 4-NO2C6H4 (5a)), were synthesized and structurally, electrochem., spectroscopically, and computationally characterized. The \textgreek{a}-diimine sections of the compds. exhibit intrachelate ring bond lengths 1.304 {\AA} {\textless} d(CN) {\textless} 1.334 and 1.425 {\AA} {\textless} d(CC) {\textless} 1.449 {\AA}, which indicate considerable metal-to-ligand charge transfer in the ground state, approaching a RuIII(BIAN.bul.-) oxidn. state formulation. The particular structural sensitivity of the strained peri-connecting C-C bond in the BIAN ligands toward metal-to-ligand charge transfer is discussed. Oxidn. of [Ru(acac)2(BIAN)] produces EPR and UV-visible-NIR (NIR = near IR) spectroelectrochem. detectable RuIII species, while the redn. yields predominantly BIAN-based spin, in agreement with d. functional theory (DFT) spin-d. calcns. Variation of the substituents from CH3 to NO2 has little effect on the spin distribution but affects the absorption spectra. Dinuclear {(μ-tppz)[Ru(Cl)(BIAN)]2}(ClO4)2, tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine; aryl (BIAN) = Ph ([1b](ClO4)2), 4-MeC6H4 ([2b](ClO4)2), 4-OMeC6H4 ([3b](ClO4)2), 4-ClC6H4 ([4b](ClO4)2), were also obtained and investigated. The structure detn. of [2b](ClO4)2 and [3b](ClO4)2 reveals trans configuration of the chloride ligands and unreduced BIAN ligands. The DFT and spectroelectrochem. results (UV-visible-NIR, EPR) indicate oxidn. to a weakly coupled RuIIIRuII mixed-valent species but redn. to a tppz-centered radical state. The effect of the \textgreek{p} electron-accepting BIAN ancillary ligands is to diminish the metal-metal interaction due to competition with the acceptor bridge tppz. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Mondal, Prasenjit and Agarwala, Hemlata and Jana, Rahul Dev and Plebst, Sebastian and Grupp, Anita and Ehret, Fabian and Mobin, Shaikh M. and Kaim, Wolfgang and Lahiri, Goutam Kumar.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2407a9f92187861fb201adf6a13b4a935/huebleriac}, doi = {10.1021/ic500730m}, interhash = {cb3fb851b57939848e82c034871e6472}, intrahash = {407a9f92187861fb201adf6a13b4a935}, issn = {0020-1669}, journal = {Inorganic Chemistry}, keywords = {DFT EPR acetylacetonato bisphenyliminoacenaphthene calcn complex complex;ruthenium crystal electrochem prepn ruthenium structure tetrakispyridylpyrazine}, number = 14, pages = {7389--7403}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Sensitivity of a Strained C-C Single Bond to Charge Transfer: Redox Activity in Mononuclear and Dinuclear Ruthenium Complexes of Bis(arylimino)acenaphthene (BIAN) Ligands}, volume = 53, year = 2014 }