%0 Journal Article %1 Das.2012c %A Das, Amit %A Scherer, Thomas Michael %A Mobin, Shaikh M. %A Kaim, Wolfgang %A Lahiri, Goutam Kumar. %D 2012 %J Inorganic Chemistry %K MO beta bipyridine complex complex;frontier complex;prepn crystal diketonate electrochem mol noninnocent optimized oxidophenalenone redox ruthenium structure %N 7 %P 4390--4397 %R 10.1021/ic300207d %T 9-Oxidophenalenone: A Noninnocent b-Diketonate Ligand? %V 51 %X The redox systems Ru(L)(bpy)2k, Ru(L)2(bpy)m, and Ru(L)3n contg. the potentially redox-active ligand 9-oxidophenalenone = L- were studied by spectroelectrochem. (UV-visible-near-IR and ESR) in conjunction with d. functional theory (DFT) calcns. Ru(L-)(bpy)2ClO4 (1ClO4) and Ru(L-)2(bpy)ClO4 (2ClO4) were structurally characterized. In addn. to establishing electron-transfer processes involving the RuII/RuIII/RuIV and bpy0/bpy·- couples, evidence for the noninnocent behavior of L- was obtained from RuIV(L·)(L-)(bpy)3+, which exhibits strong near-IR absorption due to ligand-to-ligand charge transfer. In contrast, the lability of the electrogenerated Ru(L)2(bpy)- is attributed to a resonance situation RuII(L·2-)(L-)(bpy)-/RuII(L-)2(bpy·-)-, as suggested by DFT calcns. on SciFinder(R)

@article{Das.2012c, abstract = {The redox systems [Ru(L)(bpy)2]k, [Ru(L)2(bpy)]m, and [Ru(L)3]n contg. the potentially redox-active ligand 9-oxidophenalenone = L- were studied by spectroelectrochem. (UV-visible-near-IR and ESR) in conjunction with d. functional theory (DFT) calcns. [Ru(L-)(bpy)2]ClO4 ([1]ClO4) and [Ru(L-)2(bpy)]ClO4 ([2]ClO4) were structurally characterized. In addn. to establishing electron-transfer processes involving the RuII/RuIII/RuIV and bpy0/bpy·- couples, evidence for the noninnocent behavior of L- was obtained from [RuIV(L·)(L-)(bpy)]3+, which exhibits strong near-IR absorption due to ligand-to-ligand charge transfer. In contrast, the lability of the electrogenerated [Ru(L)2(bpy)]- is attributed to a resonance situation [RuII(L·2-)(L-)(bpy)]-/[RuII(L-)2(bpy·-)]-, as suggested by DFT calcns. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Das, Amit and Scherer, Thomas Michael and Mobin, Shaikh M. and Kaim, Wolfgang and Lahiri, Goutam Kumar.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2707cd785f1deab79369ad2ded72a19d8/huebleriac}, doi = {10.1021/ic300207d}, interhash = {b2baead6248c88130decfbfe3b1d9d71}, intrahash = {707cd785f1deab79369ad2ded72a19d8}, issn = {0020-1669}, journal = {Inorganic Chemistry}, keywords = {MO beta bipyridine complex complex;frontier complex;prepn crystal diketonate electrochem mol noninnocent optimized oxidophenalenone redox ruthenium structure}, number = 7, pages = {4390--4397}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {9-Oxidophenalenone: A Noninnocent \textgreek{b}-Diketonate Ligand?}, volume = 51, year = 2012 }