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

Journal Article · Wed May 15 00:00:00 EDT 1991 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00010a013· OSTI ID:5976363

Cooper, J B; Vess, T M; Kalsbeck, W A; Wertz, D W ^[1]

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1. North Carolina State Univ., Raleigh (United States)

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.

• OSTI ID: 5976363
• Journal Information: Inorganic Chemistry; (United States), Vol. 30:10; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

14 SOLAR ENERGY
BIPYRIDINES
REDOX REACTIONS
CYANIDES
RUTHENIUM COMPLEXES
EXPERIMENTAL DATA
MOLECULAR STRUCTURE
ULTRAVIOLET SPECTRA
VISIBLE SPECTRA
AZINES
CHEMICAL REACTIONS
COMPLEXES
DATA
HETEROCYCLIC COMPOUNDS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PYRIDINES
SPECTRA
TRANSITION ELEMENT COMPLEXES
140505* - Solar Energy Conversion- Photochemical
Photobiological
& Thermochemical Conversion- (1980-)