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Formation of ((CN)/sub 5/Ru/sup II/-CN-Ru/sup III/(CN)/sub 5/)/sup 6 -/ by chemical oxidation, electrochemical oxidation, and photooxidation of Ru(CN)/sub 6//sup 4 -/

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00257a018· OSTI ID:6538467
; ;

Electron transfer to a ligand field excited state of tris(glycinato)cobalt(III) by hexacyanoruthenium(II) was observed in pH 5 acetate-buffered aqueous solution. A product of the reaction is a species that has an intervalence transfer band at 9.1 x 10/sup 3/ cm/sup -1/ (1094 nm) with a molar absorptivity of about 7 x 10/sup 3/ M/sup -1/ cm/sup -1/. The same spectroscopic band results from chemical oxidation (H/sub 2/O/sub 2/, Ce/sup 4 +/), anodic oxidation (Pt electrode), and excited-state electron transfer to tris(2,2'-bipyridine) ruthenium(II). Steady-state analysis of the kinetics of the reaction leads to an estimation of the lifetime of the excited state of tris(glycinato)cobalt(III) as 23 +/- 4 ns. The most likely species responsible for the infrared band is the cyanide-bridged dimer ((CN)/sub 5/Ru/sup II/-CN-Ru/sup III/(CN)/sub 5/)/sup 6 -/. The kinetics of its formation from hexacyanoruthenium(II) and -(III) are rapid (second-order rate constant approx. 1 x 10/sup 4/ M/sup -1/ s/sup -1/) in contrast to recent observations on nonphotochemical reactions of hexacyanoruthenium(III).

Research Organization:
Univ. of Pittsburgh, PA
OSTI ID:
6538467
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 26:10; ISSN INOCA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400400 -- Electrochemistry
400500* -- Photochemistry
ABSORPTION SPECTRA
AQUEOUS SOLUTIONS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
DISPERSIONS
ELECTROCHEMISTRY
ELECTRON TRANSFER
ENERGY LEVELS
EXCITED STATES
EXPERIMENTAL DATA
INFORMATION
KINETICS
LIGANDS
MIXTURES
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIDATION
PH VALUE
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
REACTION KINETICS
RUTHENIUM COMPLEXES
SOLUTIONS
SPECTRA
STEADY-STATE CONDITIONS
TRANSITION ELEMENT COMPLEXES
VOLTAMETRY