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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

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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
 
Creator SARKAR, B
KAIM, W
KLEIN, A
SCHWEDERSKI, B
FIEDLER, J
DUBOC-TOIA, C
LAHIRI, GK
 
Subject donor ligands
ru
chemistry
dimers
lumo
 
Description 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+).
 
Publisher AMER CHEMICAL SOC
 
Date 2011-07-15T05:10:00Z
2011-12-26T12:49:16Z
2011-12-27T05:35:05Z
2011-07-15T05:10:00Z
2011-12-26T12:49:16Z
2011-12-27T05:35:05Z
2003
 
Type Article
 
Identifier INORGANIC CHEMISTRY, 42(20), 6172-6174
0020-1669
http://dx.doi.org/10.1021/ic034105p
http://dspace.library.iitb.ac.in/xmlui/handle/10054/4161
http://hdl.handle.net/10054/4161
 
Language en