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|Title:||What a difference ancillary thienyl makes: Unexpected additional stabilization of the diruthenium(III,II) but not the diosmium(III,II) mixed-valent state in tetrazine ligand-bridged complexes|
|Publisher:||AMER CHEMICAL SOC|
|Citation:||INORGANIC CHEMISTRY, 42(20), 6172-6174|
|Abstract:||The RU2III,II Mixed-valent state is strongly stabilized in [(bpy)(2)Ru-(mu-bttz)Ru(bpy)(2)(-)](5+), (3(5+)), bttz = 3,6-bis(2-thienyl)-1,2,4,5-tetrazine, as evident from lowered oxidation potentials and isolability, a strongly increased comproportionation constant K-c = 10(16.6), and a high-energy intervalence charge transfer band at 10100 cm(-1). Curiously, no such effects were observed for the diosmium(III,II) analogue, whereas the related systems [(bpy)(2)M(mu-bmptz)M-(bPY)(2)](5+), bmptz = 3,6-bis(4-methyl-2-pyridyl)-1,2,4,5-tetrazine, exhibit conventional behavior, i.e., a slightly higher K-c value of the OS2III,II analogue. EPR signals were observed at 4 K for 3(5+) but not for the other mixed-valent species, and high-frequency (285 GHz) EPR was employed to study the diruthenium((II)) radical complexes 2(3+) and 3(3+).|
|Appears in Collections:||Article|
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