%0 Journal Article %1 Jana.2012 %A Jana, Rajkumar %A Schwederski, Brigitte %A Fiedler, Jan %A Kaim, Wolfgang. %D 2012 %J Polyhedron %K ammine benzoquinodimethane electrochem oxidn prepn redn ruthenium tetracyano tetrafluoro %N 1 %P 174--178 %R 10.1016/j.poly.2012.06.066 %T Facilitated reduction and oxidation of Ru(NH3)54(μ4-TCNX)8+ by changing from TCNX = TCNQ to TCNQF4 %V 44 %X The new tetraruthenium compd. Ru(NH3)54(μ4-TCNQF4)(PF6)8, TCNQF4 = 2,3,5,6-tetrafluoro-7,7,8,8,-tetracyano-p-benzoquinodimethane, was studied by cyclic voltammetry, IR, UV-Vis-NIR and EPR spectroelectrochem. The better p acceptor qualities of TCNQF4 in comparison to TCNQ cause more accessible redn. to produce Ru(NH3)54(μ4-TCNQF4)7+ with enhanced metal contribution to the singly occupied MO and low-energy shifted IR vibrational and NIR electronic absorptions. However, the two-electron oxidn. to the (10+) ion is also facilitated. The reason is seen in a more metal-centered oxidn. for the TCNQF4 complex while the previously studied TCNQ analog is assumed to undergo a higher degree of oxidn. at the bridging ligand. As a result, the title species has a redox potential range of only 0.52 V, indicating a significantly diminished HOMO-LUMO gap. on SciFinder(R)

@article{Jana.2012, abstract = {The new tetraruthenium compd. {[Ru(NH3)5]4(μ4-TCNQF4)}(PF6)8, TCNQF4 = 2,3,5,6-tetrafluoro-7,7,8,8,-tetracyano-p-benzoquinodimethane, was studied by cyclic voltammetry, IR, UV-Vis-NIR and EPR spectroelectrochem. The better \textgreek{p} acceptor qualities of TCNQF4 in comparison to TCNQ cause more accessible redn. to produce {[Ru(NH3)5]4(μ4-TCNQF4)}7+ with enhanced metal contribution to the singly occupied MO and low-energy shifted IR vibrational and NIR electronic absorptions. However, the two-electron oxidn. to the (10+) ion is also facilitated. The reason is seen in a more metal-centered oxidn. for the TCNQF4 complex while the previously studied TCNQ analog is assumed to undergo a higher degree of oxidn. at the bridging ligand. As a result, the title species has a redox potential range of only 0.52 V, indicating a significantly diminished HOMO-LUMO gap. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Jana, Rajkumar and Schwederski, Brigitte and Fiedler, Jan and Kaim, Wolfgang.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/218a8674abaa1414251894bb7c4d51d59/huebleriac}, doi = {10.1016/j.poly.2012.06.066}, interhash = {d097f176cbe0c63ec6fba108037bffb5}, intrahash = {18a8674abaa1414251894bb7c4d51d59}, issn = {0277-5387}, journal = {Polyhedron}, keywords = {ammine benzoquinodimethane electrochem oxidn prepn redn ruthenium tetracyano tetrafluoro}, number = 1, pages = {174--178}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Facilitated reduction and oxidation of {[Ru(NH3)5]4(μ4-TCNX)}8+ by changing from TCNX = TCNQ to TCNQF4}, volume = 44, year = 2012 }