Investigation of the redox states of (Ru(bpy) sub 2 CN) sub 2 CN sup + : Evidence for valence delocalization of the singly oxidized complex

A spectroelectrochemical study of both the oxidized and reduced forms of (Ru(bpy){sub 2}CN){sub 2}CN{sup +} is reported. The uv-vis spectra of the parent and reduced species indicate the complex consists of two identical chromophores, which are nearly identical with the Ru(bpy){sub 2}(CN){sub 2} chr...

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Bibliographic Details
Published in:Inorganic chemistry 1991-05, Vol.30:10
Main Authors: Cooper, J.B., Vess, T.M., Kalsbeck, W.A., Wertz, D.W.
Format: Article
Language:English
Subjects:
140505 - Solar Energy Conversion- Photochemical, Photobiological, & Thermochemical Conversion- (1980-)
AZINES
BIPYRIDINES
CHEMICAL REACTIONS
COMPLEXES
CYANIDES
DATA
EXPERIMENTAL DATA
HETEROCYCLIC COMPOUNDS
INFORMATION
MOLECULAR STRUCTURE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PYRIDINES
REDOX REACTIONS
RUTHENIUM COMPLEXES
SOLAR ENERGY
SPECTRA
TRANSITION ELEMENT COMPLEXES
ULTRAVIOLET SPECTRA
VISIBLE SPECTRA
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Summary:A spectroelectrochemical study of both the oxidized and reduced forms of (Ru(bpy){sub 2}CN){sub 2}CN{sup +} is reported. The uv-vis spectra of the parent and reduced species indicate the complex consists of two identical chromophores, which are nearly identical with the Ru(bpy){sub 2}(CN){sub 2} chromophore, even though one ruthenium is bound to the carbon of the bridging CN while the other is nitrogen bound. Only the shift in the bridging CN stretching frequency wit reduction offers any distinction between the two following observations: (1) only two CN stretches are observed in the oxidized form, (2) the shift to higher energy of the terminal CN stretches for the bimetallic species is half of that observed upon oxidation of the monometallic complex, (3) the sharpness and solvent independence of the near-IR band is not consistent with Hush predictions for the IVT band, and (4) the separation of the oxidation waves implies a comproportionation constant for the bimetallic species of 1.38 {times} 10{sup 10} (assuming no difference in metal centers) comparable in magnitude to other delocalized systems. 40 refs., 8 figs., 2 tabs.
ISSN:0020-1669
1520-510X
DOI:10.1021/ic00010a013