%0 Journal Article %1 Mandal.2015b %A Mandal, Abhishek %A Schwederski, Brigitte %A Fiedler, Jan %A Kaim, Wolfgang %A Lahiri, Goutam Kumar. %D 2015 %J Inorganic Chemistry %K acac bipyridine complex complex;mol complex;prepn complex;redox crystal formazanato mononuclear noninnocent property ruthenium structure %N 16 %P 8126--8135 %R 10.1021/acs.inorgchem.5b01408 %T Evidence for Bidirectional Noninnocent Behavior of a Formazanate Ligand in Ruthenium Complexes %V 54 %X Redox series of the complexes Ru(L)(L')2n, L = 1,5-diphenyl-3-(4-tolyl)-formazanate and L' = 2,4-pentanedionate (acac-), 2,2'-bipyridine (bpy), or 2-phenylazopyridine (pap), were studied by cyclic and differential pulse voltammetry and by TD-DFT-supported spectroelectrochem. (UV-visible-NIR, EPR). The prepd. complexes are Ru(L-)(acac)2 (1), Ru(L-)(bpy)2(ClO4) (2) , and Ru(L-)(bpy)2(ClO4) (3). The precursors RuIII(L-)(acac-)2, RuII(L-)(bpy)2ClO4, and RuII(L-)(pap)2ClO4 were identified in their indicated oxidn. states by x-ray crystal structure detn. The six-membered formazanato-ruthenium chelate rings have an envelope conformation with puckering of the metal. DFT calcns. indicate a pronounced sensitivity of the N-N bond lengths toward the ligand oxidn. state. Several electrochem. accessible charge states were analyzed, and the derived oxidn. nos. RuII, RuIII, or RuIV, L' or (L').bul.-, and L-, L.bul.2-, or the new formazanyl ligand L.bul. for the two-way noninnocent formazanate reflect the increasing acceptor effect of the ancillary ligands L' in the series acac- \textless bpy \textless pap. on SciFinder(R)

@article{Mandal.2015b, abstract = {Redox series of the complexes [Ru(L)(L')2]n, L = 1,5-diphenyl-3-(4-tolyl)-formazanate and L' = 2,4-pentanedionate (acac-), 2,2'-bipyridine (bpy), or 2-phenylazopyridine (pap), were studied by cyclic and differential pulse voltammetry and by TD-DFT-supported spectroelectrochem. (UV-visible-NIR, EPR). The prepd. complexes are [Ru(L-)(acac)2] (1), [Ru(L-)(bpy)2](ClO4) (2) , and [Ru(L-)(bpy)2](ClO4) (3). The precursors [RuIII(L-)(acac-)2], [RuII(L-)(bpy)2]ClO4, and [RuII(L-)(pap)2]ClO4 were identified in their indicated oxidn. states by x-ray crystal structure detn. The six-membered formazanato-ruthenium chelate rings have an envelope conformation with puckering of the metal. DFT calcns. indicate a pronounced sensitivity of the N-N bond lengths toward the ligand oxidn. state. Several electrochem. accessible charge states were analyzed, and the derived oxidn. nos. RuII, RuIII, or RuIV, L' or (L').bul.-, and L-, L.bul.2-, or the new formazanyl ligand L.bul. for the two-way noninnocent formazanate reflect the increasing acceptor effect of the ancillary ligands L' in the series acac- {\textless} bpy {\textless} pap. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Mandal, Abhishek and Schwederski, Brigitte and Fiedler, Jan and Kaim, Wolfgang and Lahiri, Goutam Kumar.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/24649810b900436c3ca29938481d0c1db/huebleriac}, doi = {10.1021/acs.inorgchem.5b01408}, interhash = {24a06ed89464cb9d9ee019461b955a61}, intrahash = {4649810b900436c3ca29938481d0c1db}, issn = {0020-1669}, journal = {Inorganic Chemistry}, keywords = {acac bipyridine complex complex;mol complex;prepn complex;redox crystal formazanato mononuclear noninnocent property ruthenium structure}, number = 16, pages = {8126--8135}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Evidence for Bidirectional Noninnocent Behavior of a Formazanate Ligand in Ruthenium Complexes}, volume = 54, year = 2015 }