%0 Journal Article %1 Das.2012e %A Das, Amit %A Scherer, Thomas Michael %A Mondal, Prasenjit %A Mobin, Shaikh M. %A Kaim, Wolfgang %A Lahiri, Goutam Kumar. %D 2012 %J Chemistry - A European Journal %K calcn complex complex;ruthenium cyclic diketonate electron exchange ligand noninnocent oxidophenalenone oxidophenalenone;DFT oxidophenalenone;EPR oxidophenalenone;noninnocence phenylazopyridine prepn ruthenium voltammetry %N 45 %P 14434-14443, S14434/1-S14434/24 %R 10.1002/chem.201201785 %T Experimental- and DFT Evidence for the Fractional Non-Innocence of a b-Diketonate Ligand %V 18 %X Ru(pap)2(L)(ClO4), Ru(pap)(L)2, and Ru(acac)2(L) (pap = 2-phenylazopyridine, L- = 9-oxidophenalenone, acac- = 2,4-pentanedionate) were prepd. and studied regarding their electron-transfer behavior, both exptl. and by using DFT calcns. Ru(pap)2(L)(ClO4) and Ru(acac)2(L) were characterized by crystal-structure anal. Spectroelectrochem. (EPR, UV/visible/NIR), in conjunction with cyclic voltammetry, showed a wide range of $\sim$2 V for the potential of the RuIII/II couple, which was in agreement with the very different characteristics of the strongly p-accepting pap ligand and the s-donating acac- ligand. At the rather high potential of +1.35 V vs. SCE, the oxidn. of L- into L.bul. could be deduced from the near-IR absorption of RuIII(pap)(L.bul.)(L-)2+. Other intense long-wavelength transitions, including LMCT (L-$\rightarrow$RuIII) and LL/CT (pap.bul.-$\rightarrow$L-) processes, were confirmed by TD-DFT results. DFT calcns. and EPR data for the paramagnetic intermediates allowed the authors to assess the spin densities, which revealed two cases with considerable contributions from L-radical-involving forms, i.e., RuIII(pap0)2(L-)2+$łeftrightarrow$RuII(pap0)2(L.bul.)2+ and RuIII(pap0)(L-)2+$łeftrightarrow$RuII(pap0)(L.bul.)(L-)+. Calcns. of electrogenerated RuII(pap.bul.-)(pap0)(L-) displayed considerable neg. spin d. (-0.188) at the bridging metal. on SciFinder(R)

@article{Das.2012e, abstract = {[Ru(pap)2(L)](ClO4), [Ru(pap)(L)2], and [Ru(acac)2(L)] (pap = 2-phenylazopyridine, L- = 9-oxidophenalenone, acac- = 2,4-pentanedionate) were prepd. and studied regarding their electron-transfer behavior, both exptl. and by using DFT calcns. [Ru(pap)2(L)](ClO4) and [Ru(acac)2(L)] were characterized by crystal-structure anal. Spectroelectrochem. (EPR, UV/visible/NIR), in conjunction with cyclic voltammetry, showed a wide range of $\sim$2 V for the potential of the RuIII/II couple, which was in agreement with the very different characteristics of the strongly \textgreek{p}-accepting pap ligand and the \textgreek{s}-donating acac- ligand. At the rather high potential of +1.35 V vs. SCE, the oxidn. of L- into L.bul. could be deduced from the near-IR absorption of [RuIII(pap)(L.bul.)(L-)]2+. Other intense long-wavelength transitions, including LMCT (L-$\rightarrow$RuIII) and LL/CT (pap.bul.-$\rightarrow$L-) processes, were confirmed by TD-DFT results. DFT calcns. and EPR data for the paramagnetic intermediates allowed the authors to assess the spin densities, which revealed two cases with considerable contributions from L-radical-involving forms, i.e., [RuIII(pap0)2(L-)]2+$\leftrightarrow$[RuII(pap0)2(L.bul.)]2+ and [RuIII(pap0)(L-)2]+$\leftrightarrow$[RuII(pap0)(L.bul.)(L-)]+. Calcns. of electrogenerated [RuII(pap.bul.-)(pap0)(L-)] displayed considerable neg. spin d. (-0.188) at the bridging metal. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Das, Amit and Scherer, Thomas Michael and Mondal, Prasenjit and Mobin, Shaikh M. and Kaim, Wolfgang and Lahiri, Goutam Kumar.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/235b5d8efb6b3707e118f219fd9a63de0/huebleriac}, doi = {10.1002/chem.201201785}, interhash = {a5b3b8e44467c442d45d386e38c740e5}, intrahash = {35b5d8efb6b3707e118f219fd9a63de0}, issn = {0947-6539}, journal = {Chemistry - A European Journal}, keywords = {calcn complex complex;ruthenium cyclic diketonate electron exchange ligand noninnocent oxidophenalenone oxidophenalenone;DFT oxidophenalenone;EPR oxidophenalenone;noninnocence phenylazopyridine prepn ruthenium voltammetry}, number = 45, pages = {14434-14443, S14434/1-S14434/24}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Experimental- and DFT Evidence for the Fractional Non-Innocence of a \textgreek{b}-Diketonate Ligand}, volume = 18, year = 2012 }