%0 Journal Article %1 Baumann.1998 %A Baumann, Frank %A Kaim, Wolfgang %A Posse, Monica Garcia %A Katz, Nestor E. %D 1998 %J Inorganic Chemistry %K ESR ammine ammine;oxidn bipyrimidine dinuclear;redn dinuclear;spectroelectrochem electrochem electrogenerated multistep redox ruthenium %N 4 %P 658--660 %R 10.1021/IC971143Y %T Spectroelectrochemistry of the Multistep Redox System (μ-bpym)Ru(NH3)42n+, n = 2-6, in a Nonaqueous Medium %V 37 %X Dinuclear (μ-bpym)Ru(NH3)424+ (bpym = 2,2'-bipyrimidine), isolated as the tetrakis(hexafluorophosphate) salt, undergoes two reversible oxidn. and two reversible redn. processes in dry acetonitrile/0.1M Bu4NPF6. The more accessible 3+, 4+, and 5+ states were characterized spectroelectrochem. (UV/visible/NIR). The EPR-active 3+ form (g1 = 2.0089, g2 = 1.9967, g = 1.9308, 〈g〉 = 1.9785) is best described as a complex between the bpym radical anion and two tetraammineruthenium(II) fragments. The 5+ state, however, is EPR silent down to 3.5 K due to rapid relaxation involving metal-based orbitals; it exhibits a weak absorption in the 3200 cm-1 region which may be assocd. with the intervalence-transfer (IT) transition. Although the question of (de)localization in the mixed-valent 5+ species cannot be answered the comproportionation const. of 105.1 signifies strong metal-metal interaction under these conditions. on SciFinder(R)

@article{Baumann.1998, abstract = {Dinuclear {(μ-bpym)[Ru(NH3)4]2}4+ (bpym = 2,2'-bipyrimidine), isolated as the tetrakis(hexafluorophosphate) salt, undergoes two reversible oxidn. and two reversible redn. processes in dry acetonitrile/0.1M Bu4NPF6. The more accessible 3+, 4+, and 5+ states were characterized spectroelectrochem. (UV/visible/NIR). The EPR-active 3+ form (g1 = 2.0089, g2 = 1.9967, g = 1.9308, 〈g〉 = 1.9785) is best described as a complex between the bpym radical anion and two tetraammineruthenium(II) fragments. The 5+ state, however, is EPR silent down to 3.5 K due to rapid relaxation involving metal-based orbitals; it exhibits a weak absorption in the 3200 cm-1 region which may be assocd. with the intervalence-transfer (IT) transition. Although the question of (de)localization in the mixed-valent 5+ species cannot be answered the comproportionation const. of 105.1 signifies strong metal-metal interaction under these conditions. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Baumann, Frank and Kaim, Wolfgang and Posse, Monica Garcia and Katz, Nestor E.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2675bbff644761fb36a34e97979464a7e/huebleriac}, doi = {10.1021/IC971143Y}, interhash = {e0c838c200e22719d99e86b534b452c7}, intrahash = {675bbff644761fb36a34e97979464a7e}, issn = {0020-1669}, journal = {Inorganic Chemistry}, keywords = {ESR ammine ammine;oxidn bipyrimidine dinuclear;redn dinuclear;spectroelectrochem electrochem electrogenerated multistep redox ruthenium}, number = 4, pages = {658--660}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Spectroelectrochemistry of the Multistep Redox System {(μ-bpym)[Ru(NH3)4]2}n+, n = 2-6, in a Nonaqueous Medium}, volume = 37, year = 1998 }