%0 Journal Article %1 Kaim.1990f %A Kaim, Wolfgang %A Kasack, Volker. %D 1990 %J Inorganic Chemistry %K HOMO acceptor d5 d6 dimer donor ligand orbital;LUMO osmium rule ruthenium stability;stability %N 23 %P 4696--4699 %R 10.1021/ic00348a022 %T Stability rules for d5/d6 mixed-valent dimers. Effects from the donor/acceptor capability of the metal (ruthenium vs osmium) and from the occupancy of the mediating ligand orbital (LUMO vs HOMO) %V 29 %X Electrochem. stability consts. were detd. for the mixed-valent intermediates in the redox series (bpy)2M(bptz)M(bpy)24+/5+/6+ and (bpy)2M(adc-Me2-)M(bpy)22+/3+/4+; M = Ru, Os; bptz = 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine, adc-Me2- = 1,2-diacetylhydrazido(2-), bpy = 2,2'-bipyridine. The trends obsd. allow the rationalization, in a consistent fashion, the stability of the mixed-valence forms toward disproportionation: The equil. const. Kc depends on the p-donor/p-acceptor character of the metals and on the occupancy and electron population at the coordinating centers of the interacting ligand p orbital. Recent literature examples support this more practically oriented concept, which can be used in the design of new stable mixed-valent complexes. on SciFinder(R)

@article{Kaim.1990f, abstract = {Electrochem. stability consts. were detd. for the mixed-valent intermediates in the redox series [(bpy)2M(bptz)M(bpy)2]4+/5+/6+ and [(bpy)2M(adc-Me2-)M(bpy)2]2+/3+/4+; M = Ru, Os; bptz = 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine, adc-Me2- = 1,2-diacetylhydrazido(2-), bpy = 2,2'-bipyridine. The trends obsd. allow the rationalization, in a consistent fashion, the stability of the mixed-valence forms toward disproportionation: The equil. const. Kc depends on the \textgreek{p}-donor/\textgreek{p}-acceptor character of the metals and on the occupancy and electron population at the coordinating centers of the interacting ligand \textgreek{p} orbital. Recent literature examples support this more practically oriented concept, which can be used in the design of new stable mixed-valent complexes. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Kaim, Wolfgang and Kasack, Volker.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2c64e248c1e27909f644d2fe32a3f6d86/huebleriac}, doi = {10.1021/ic00348a022}, interhash = {d2bd4806cc8476b27888f9cf64d56e84}, intrahash = {c64e248c1e27909f644d2fe32a3f6d86}, issn = {0020-1669}, journal = {Inorganic Chemistry}, keywords = {HOMO acceptor d5 d6 dimer donor ligand orbital;LUMO osmium rule ruthenium stability;stability}, number = 23, pages = {4696--4699}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Stability rules for d5/d6 mixed-valent dimers. Effects from the donor/acceptor capability of the metal (ruthenium vs osmium) and from the occupancy of the mediating ligand orbital (LUMO vs HOMO)}, volume = 29, year = 1990 }