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Electrochemical and spectral investigations of ring-substituted bipyridine complexes of ruthenium

Journal Article · · J. Am. Chem. Soc.; (United States)
DOI:https://doi.org/10.1021/ja00390a022· OSTI ID:6205063
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A spectroelectrochemical study of Ru complexes has been carried out using an optically transparent thin-layer electrode (OTTLE). The visible spectra of the reduced complexes Ru(Bpa5COOEt)/sub 3//sup n/(Bp5COOEt = 5,5'-bis-(ethoxycarbonyl)-2,2'-bipyridine) and Ru(bpy)/sub 3//sup n/(bpy = bipyridine) resemble the spectra of the corresponding ligand radical anion whereas the spectrum of Ru(Bp4COOEt)/sub 3//sup n/(Bp4COOet = 4,4'-bis(ethoxycarbonyl)-2,2'-bipyridine) does not. In the near-IR two types of spectral behavior are observed once the complexes are reduced beyond the 2+ oxidation state: Type A complexes (e.g., Ru(bpy)/sub 3/, Ru(Bp4Me)/sub 3/ (Bp4Me = 4,4'-dimethyl-2,2'-bipyridine)) exhibit low-intensity (epsilon < 2500) bands similar to the spectra of the reduced free ligand. Type B complexes (e.g., Ru(Bp4COOEt)/sub 3//sup n/, Ru(Bp4CONEt/sub 2/)/sub 3//sup n/ (Bp4CONEt/sub 2/ = 4,4'-bis(diethylcarbamyl)-2,2'-bipyridine)) exhibit broad bands of greater intensity (1000 < epsilon < 15,000). Possible origins for type B behavior are discussed. Electrochemical results reveal an almost perfect linear correlation between ligand reduction potentials and the 2+/1+ couple of the corresponding ruthenium complex (correlation coefficient = 0.9993). The thermodynamic implications of this observation are considered. These data support a model of the reduced metal complex having electrons localized in ligand orbitals.

Research Organization:
Colorado State Univ., Fort Collins
DOE Contract Number:
AC02-80ER10589
OSTI ID:
6205063
Journal Information:
J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 104:26; ISSN JACSA
Country of Publication:
United States
Language:
English

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Related Subjects

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AZINES
BIPYRIDINES
CHEMICAL PREPARATION
CHEMISTRY
COMPARATIVE EVALUATIONS
COMPLEXES
DATA
ELECTROCHEMISTRY
ELECTRONIC STRUCTURE
ENERGY LEVELS
EXCITED STATES
EXPERIMENTAL DATA
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
HETEROCYCLIC COMPOUNDS
INFORMATION
IRON COMPLEXES
LIGANDS
MULTIPLETS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOSPHORUS COMPOUNDS
PHOSPHORUS FLUORIDES
PYRIDINES
REDOX POTENTIAL
RUTHENIUM COMPLEXES
SPECTRA
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
TRIPLETS
VISIBLE SPECTRA
VOLTAMETRY