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
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Creator |
SARKAR, B
KAIM, W KLEIN, A SCHWEDERSKI, B FIEDLER, J DUBOC-TOIA, C LAHIRI, GK |
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Subject |
donor ligands
ru chemistry dimers lumo |
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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+).
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Publisher |
AMER CHEMICAL SOC
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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 |
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Type |
Article
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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 |
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Language |
en
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