Sarkar, Biprajit ; Kaim, Wolfgang ; Klein, Axel ; Schwederski, Brigitte ; Fiedler, Jan ; Duboc-Toia, Carole ; Lahiri, Goutam K. (2003) 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 Inorganic Chemistry, 42 (20). pp. 6172-6174. ISSN 0020-1669
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Official URL: http://pubs.acs.org/doi/abs/10.1021/ic034105p
Related URL: http://dx.doi.org/10.1021/ic034105p
Abstract
The Ru2III,II mixed-valent state is strongly stabilized in [(bpy)2Ru(μ-bttz)Ru(bpy)2]5+ (35+), bttz = 3,6-bis(2-thienyl)-1,2,4,5-tetrazine, as evident from lowered oxidation potentials and isolability, a strongly increased comproportionation constant Kc = 1016.6, 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)2M(μ-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 Kc value of the Os2III,II analogue. EPR signals were observed at 4 κ for 35+ but not for the other mixed-valent species, and high-frequency (285 GHz) EPR was employed to study the diruthenium(II) radical complexes 23+ and 33+.
| Item Type: | Article |
|---|---|
| Source: | Copyright of this article belongs to American Chemical Society. |
| ID Code: | 88405 |
| Deposited On: | 28 Mar 2012 10:00 |
| Last Modified: | 28 Mar 2012 10:00 |
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