%0 Journal Article %1 Mondal.2018 %A Mondal, Sudipta %A Schwederski, Brigitte %A Frey, Wolfgang %A Fiedler, Jan %A Zalis, Stanislav %A Kaim, Wolfgang. %D 2018 %J Inorganic Chemistry %K DFT active;ruthenium analysis bridge charge complex;mixed crystal diruthenium prepn radical redox ruthenium salicyloylhydrazide spectroelectrochem state structure tertbutylterpyridine valency %N 7 %P 3983--3992 %R 10.1021/acs.inorgchem.8b00173 %T At the Borderline between Metal-Metal Mixed Valency and a Radical Bridge Situation: Four Charge States of a Diruthenium Complex with a Redox-Active Bis(mer-tridentate) Ligand %V 57 %X L3Ru(m,h3:h3-BL)RuL3n+ (1n+, L3 = 4,4',4''-tri-tert-butyl-2,6,2',6''-terpyridine and H2BL2- = 1,2-bis(salicyloyl)hydrazide(2-)) were isolated with PF6- or ClO4- counterions (n = 1) and as bis(hexafluorophosphate) (n = 2). Structural, electrochem., and spectroscopic characterization reveals the monocation as intermediate (Kc = 108.2) in the three-step reversible redox system 10/+/2+/3+. The 1+ ion has the mol.-bridged (Ru- - -Ru 4.727 \AA) Ru centers involved in five- and six-membered chelate rings, and it exhibits long-wavelength absorptions at lmax 2240, 1660, and 1530 nm (emax = 1000, 3000, and 8000 M-1 cm-1, resp.), which would be compatible with a RuIIIRuII mixed-valent situation or with a coordinated radical ion bridge. In fact, EPR and DFT anal. of 1+ reveals that the spin is equally distributed over the ligand bridge and over both metals. The oxidized paramagnetic ions 12+ and 13+ were studied by 1H NMR and EPR and by TD-DFT supported UV-visible-NIR and MIR (mid-IR) spectroelectrochem. The capacity of various kinds of bis(mer-tridentate) bridging ligands (p donors or p acceptors, cyclometalated or noncyclometalated) for mediating metal-metal interactions is discussed. on SciFinder(R)

@article{Mondal.2018, abstract = {[L3Ru(\textgreek{m},\textgreek{h}3:\textgreek{h}3-BL)RuL3]n+ (1n+, L3 = 4,4',4''-tri-tert-butyl-2,6,2',6''-terpyridine and H2BL2- = 1,2-bis(salicyloyl)hydrazide(2-)) were isolated with PF6- or ClO4- counterions (n = 1) and as bis(hexafluorophosphate) (n = 2). Structural, electrochem., and spectroscopic characterization reveals the monocation as intermediate (Kc = 108.2) in the three-step reversible redox system 10/+/2+/3+. The 1+ ion has the mol.-bridged (Ru- - -Ru 4.727 {\AA}) Ru centers involved in five- and six-membered chelate rings, and it exhibits long-wavelength absorptions at \textgreek{l}max 2240, 1660, and 1530 nm (\textgreek{e}max = 1000, 3000, and 8000 M-1 cm-1, resp.), which would be compatible with a RuIIIRuII mixed-valent situation or with a coordinated radical ion bridge. In fact, EPR and DFT anal. of 1+ reveals that the spin is equally distributed over the ligand bridge and over both metals. The oxidized paramagnetic ions 12+ and 13+ were studied by 1H NMR and EPR and by TD-DFT supported UV-visible-NIR and MIR (mid-IR) spectroelectrochem. The capacity of various kinds of bis(mer-tridentate) bridging ligands (\textgreek{p} donors or \textgreek{p} acceptors, cyclometalated or noncyclometalated) for mediating metal-metal interactions is discussed. [on SciFinder(R)]}, added-at = {2019-07-15T13:41:23.000+0200}, author = {Mondal, Sudipta and Schwederski, Brigitte and Frey, Wolfgang and Fiedler, Jan and Zalis, Stanislav and Kaim, Wolfgang.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/278609dcc615d80235e9bbb6ba34db453/b_schwederski}, doi = {10.1021/acs.inorgchem.8b00173}, interhash = {c89dd79971fb03cc0f1ac4a19bb3fc23}, intrahash = {78609dcc615d80235e9bbb6ba34db453}, issn = {0020-1669}, journal = {Inorganic Chemistry}, keywords = {DFT active;ruthenium analysis bridge charge complex;mixed crystal diruthenium prepn radical redox ruthenium salicyloylhydrazide spectroelectrochem state structure tertbutylterpyridine valency}, number = 7, pages = {3983--3992}, timestamp = {2019-07-15T11:42:10.000+0200}, title = {At the Borderline between Metal-Metal Mixed Valency and a Radical Bridge Situation: Four Charge States of a Diruthenium Complex with a Redox-Active Bis(mer-tridentate) Ligand}, volume = 57, year = 2018 }