%0 Journal Article %1 Agarwala.2014 %A Agarwala, Hemlata %A Scherer, Thomas Michael %A Mobin, Shaikh M. %A Kaim, Wolfgang %A Lahiri, Goutam Kumar. %D 2014 %J Dalton Transactions %K DFT DMSO calcn complex crystal electrochem electronic oxidophenalenone prepn ruthenium structure structure;ruthenium trithiacyclononane %N 10 %P 3939--3948 %R 10.1039/c3dt53069h %T Bidirectional non-innocence of the b-diketonato ligand 9-oxidophenalenone (L-) in Ru(9aneS3)(L)(dmso)n, 9aneS3 = 1,4,7-trithiacyclononane %V 43 %X RuII(9aneS3)(L)(DMSO)ClO4 (1ClO4) (9aneS3 = 1,4,7-trithiacyclononane, HL = 9-hydroxyphenalenone, DMSO = DMSO) was structurally characterized to reveal almost equal C-O bond distances of coordinated L-, suggesting a delocalized bonding situation of the b-diketonato ligand. The DMSO ligand is coordinated via the sulfur atom in the native (1+) and reduced states (1 and 1-) as was revealed by x-ray crystallog. and by DFT calcns. Cyclic voltammetry of 1+ exhibits two close-lying 1-electron oxidn. waves at 0.77 V and 0.94 V, and two similarly close 1-electron redn. processes at -1.43 V and -1.56 V vs. SCE in CH2Cl2. The electronic structures of 1n in the accessible redox states were analyzed via expts. (EPR and UV-visible-NIR spectroelectrochem.) and by DFT/TD-DFT calcns., revealing the potential for bidirectional noninnocent behavior of coordinated L·/-/·2-. Specifically, the studies establish significant involvement of L based frontier orbitals in both the oxidn. and redn. processes: (9aneS3)(DMSO)RuIII-L·3+ (13+) .dblharw. (9aneS3)(DMSO)RuIII-L-2+/(9aneS3)(DMSO)RuII-L·2+ (12+) .dblharw. (9aneS3)(DMSO)RuII-L-+ (1+) .dblharw. (9aneS3)(DMSO)RuII-L·2- (1) .dblharw. (9aneS3)(DMSO)RuII-L3--/(9aneS3)(DMSO)RuI-L·2-- (1-). on SciFinder(R)

@article{Agarwala.2014, abstract = {[RuII([9]aneS3)(L)(DMSO)]ClO4 ([1]ClO4) ([9]aneS3 = 1,4,7-trithiacyclononane, HL = 9-hydroxyphenalenone, DMSO = DMSO) was structurally characterized to reveal almost equal C-O bond distances of coordinated L-, suggesting a delocalized bonding situation of the \textgreek{b}-diketonato ligand. The DMSO ligand is coordinated via the sulfur atom in the native (1+) and reduced states (1 and 1-) as was revealed by x-ray crystallog. and by DFT calcns. Cyclic voltammetry of 1+ exhibits two close-lying 1-electron oxidn. waves at 0.77 V and 0.94 V, and two similarly close 1-electron redn. processes at -1.43 V and -1.56 V vs. SCE in CH2Cl2. The electronic structures of 1n in the accessible redox states were analyzed via expts. (EPR and UV-visible-NIR spectroelectrochem.) and by DFT/TD-DFT calcns., revealing the potential for bidirectional noninnocent behavior of coordinated L·/-/·2-. Specifically, the studies establish significant involvement of L based frontier orbitals in both the oxidn. and redn. processes: [([9]aneS3)(DMSO)RuIII-L·]3+ (13+) .dblharw. [([9]aneS3)(DMSO)RuIII-L-]2+/[([9]aneS3)(DMSO)RuII-L·]2+ (12+) .dblharw. [([9]aneS3)(DMSO)RuII-L-]+ (1+) .dblharw. [([9]aneS3)(DMSO)RuII-L·2-] (1) .dblharw. [([9]aneS3)(DMSO)RuII-L3-]-/[([9]aneS3)(DMSO)RuI-L·2-]- (1-). [on SciFinder(R)]}, added-at = {2019-07-15T13:41:23.000+0200}, author = {Agarwala, Hemlata and Scherer, Thomas Michael and Mobin, Shaikh M. and Kaim, Wolfgang and Lahiri, Goutam Kumar.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2e802c161b7cc45f2657ed131de6edf11/b_schwederski}, doi = {10.1039/c3dt53069h}, interhash = {3c9b8bdfbc47392b13d0dee1b89f0242}, intrahash = {e802c161b7cc45f2657ed131de6edf11}, issn = {1477-9226}, journal = {Dalton Transactions}, keywords = {DFT DMSO calcn complex crystal electrochem electronic oxidophenalenone prepn ruthenium structure structure;ruthenium trithiacyclononane}, number = 10, pages = {3939--3948}, timestamp = {2019-07-15T11:42:10.000+0200}, title = {Bidirectional non-innocence of the \textgreek{b}-diketonato ligand 9-oxidophenalenone (L-) in [Ru([9]aneS3)(L)(dmso)]n, [9]aneS3 = 1,4,7-trithiacyclononane}, volume = 43, year = 2014 }