%0 Journal Article %1 Mandal.2014b %A Mandal, Abhishek %A Kundu, Tanaya %A Ehret, Fabian %A Bubrin, Martina %A Mobin, Shaikh M. %A Kaim, Wolfgang %A Lahiri, Goutam Kumar. %D 2014 %J Dalton Transactions %K MO acetylacetonato complex crystal electrochem ground magnetism;DFT phenanthrenequinonoid prepn ruthenium state structure %N 6 %P 2473--2487 %R 10.1039/C3DT53104J %T Varying electronic structural forms of ruthenium complexes of non-innocent 9,10-phenanthrenequinonoid ligands %V 43 %X Bis(acetylacetonato)ruthenium complexes [Ru(acac)2(Q1-3)], 1-3, incorporating redox non-innocent 9,10-phenanthrenequinonoid ligands (Q1 = 9,10-phenanthrenequinone, 1; Q2 = 9,10-phenanthrenequinonediimine, 2; Q3 = 9,10-phenanthrenequinonemonoimine, 3) were characterized electrochem., spectroscopically and structurally. The four independent mols. in the unit cell of 2 are involved in intermol. hydrogen bonding and p-p interactions, leading to a 2D network. The oxidn. state-sensitive bond distances of the coordinated ligands Qn at 1.296(5)/1.289(5) \AA (C-O), 1.315(3)/1.322(4) \AA (C-N), and 1.285(3)/1.328(3) \AA (C-O/C-N) in 1, 2 and 3, resp., and the well resolved 1H NMR resonances within the std. chem. shift range suggest DFT supported variable contributions from valence formulations [RuIII(acac)2(Q*-)] (spin-coupled) and [RuII(acac)2(Q0)], resp. Complexes 1-3 exhibit one oxidn. and two redn. steps with comproportionation consts. Kc $\sim$ 107-1022 for the intermediates. The electrochem. generated persistent redox states 1n (n = 0, 1-, 2-) and 2n/3n (n = 1+, 0, 1-, 2-) were analyzed by UV-visible-NIR spectroelectrochem. and by EPR for the paramagnetic intermediates in combination with DFT and TD-DFT calcns., revealing significant differences in the oxidn. state distribution at the Ru-Q interface for 1n-3n. In particular, the diminished propensity of the NH-contg. systems for redn. results in the preference for RuII(Q0) relative to RuIII(Q*-) (neutral compds.) and for RuII(Q*-) over the RuIII(Q2-) alternative in the case of the monoanionic complexes. [on SciFinder(R)]

@article{Mandal.2014b, abstract = {Bis(acetylacetonato)ruthenium complexes [Ru(acac)2(Q1-3)], 1-3, incorporating redox non-innocent 9,10-phenanthrenequinonoid ligands (Q1 = 9,10-phenanthrenequinone, 1; Q2 = 9,10-phenanthrenequinonediimine, 2; Q3 = 9,10-phenanthrenequinonemonoimine, 3) were characterized electrochem., spectroscopically and structurally. The four independent mols. in the unit cell of 2 are involved in intermol. hydrogen bonding and \textgreek{p}-\textgreek{p} interactions, leading to a 2D network. The oxidn. state-sensitive bond distances of the coordinated ligands Qn at 1.296(5)/1.289(5) {\AA} (C-O), 1.315(3)/1.322(4) {\AA} (C-N), and 1.285(3)/1.328(3) {\AA} (C-O/C-N) in 1, 2 and 3, resp., and the well resolved 1H NMR resonances within the std. chem. shift range suggest DFT supported variable contributions from valence formulations [RuIII(acac)2(Q*-)] (spin-coupled) and [RuII(acac)2(Q0)], resp. Complexes 1-3 exhibit one oxidn. and two redn. steps with comproportionation consts. Kc $\sim$ 107-1022 for the intermediates. The electrochem. generated persistent redox states 1n (n = 0, 1-, 2-) and 2n/3n (n = 1+, 0, 1-, 2-) were analyzed by UV-visible-NIR spectroelectrochem. and by EPR for the paramagnetic intermediates in combination with DFT and TD-DFT calcns., revealing significant differences in the oxidn. state distribution at the {Ru-Q} interface for 1n-3n. In particular, the diminished propensity of the NH-contg. systems for redn. results in the preference for RuII(Q0) relative to RuIII(Q*-) (neutral compds.) and for RuII(Q*-) over the RuIII(Q2-) alternative in the case of the monoanionic complexes. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Mandal, Abhishek and Kundu, Tanaya and Ehret, Fabian and Bubrin, Martina and Mobin, Shaikh M. and Kaim, Wolfgang and Lahiri, Goutam Kumar.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2ee2094634d915e93c505fae7097f5547/huebleriac}, doi = {10.1039/C3DT53104J}, interhash = {470e8a4cd2481bdcd22ca7e32f0ca928}, intrahash = {ee2094634d915e93c505fae7097f5547}, issn = {1477-9226}, journal = {Dalton Transactions}, keywords = {MO acetylacetonato complex crystal electrochem ground magnetism;DFT phenanthrenequinonoid prepn ruthenium state structure}, number = 6, pages = {2473--2487}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Varying electronic structural forms of ruthenium complexes of non-innocent 9,10-phenanthrenequinonoid ligands}, volume = 43, year = 2014 }