Hydride transfer in the oxidation of formate ion by ((bpy)/sub 2/(py)Ru(O))/sup 2 +/

Journal Article · Wed Jul 09 00:00:00 EDT 1986 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00274a035· OSTI ID:5582913

Roecker, L; Meyer, T J

The kinetics of oxidation of formic acid/formate ion by ((bpy)/sub 2/(py)Ru/sup IV/(O))/sup 2 +/ (bpy is 2,2'-bipyridine and py is pyridine) have been studied as a function of pH and temperature, and the kinetics of oxidation of HCO/sub 2//sup -/ by ((bpy)/sub 2/(py)-Ru/sup III/(OH))/sup 2 +/ have been studied at pH 7. The pH dependence of the Ru/sup IV/ reaction is consistent with paths involving oxidation of HCO/sub 2/H, k (25/sup 0/C, ..mu.. = 0.1 M) = 0.01 +/- 0.04 M/sup -1/ s/sup -1/, and of HCO/sub 2//sup -/, k (25/sup 0/C, ..mu.. = 0.1 M) = 4.2 +/- 0.2 M/sup -1/ s/sup -1/. For the oxidation of HCO/sub 2//sup -/ by Ru/sup III/, k (25/sup 0/C, ..mu.. = 1.0 M, pH 7) = 0.01 M/sup -1/s/sup -1/. The path involving Ru/sup IV/ and HCO/sub 2//sup -/ exhibits a large kinetic isotope effect with k/sub HCO/sub 2//sup -///k/sub DCO/sub 2//sup -// = 19 (25/sup 0/C, ..mu.. = 1.0 M) while that involving Ru/sup III/ and HVO/sub 2//sup -/ has a much smaller kinetic isotope effect with k/sub HCO/sub 2//sup -///k/sub DCO/sub 2//sup -// = 3 (25/sup 0/C, ..mu.. 1.0 M). Spectral evidence, in conjunction with the isotope effect data, suggests that oxidation of HCO/sub 2//sup -/ by ((bpy)/sub 2/(py)Ru/sup IV/(O))/sup 2 +/ occurs by a two-electron, hydride transfer which is discussed in some detail. Oxidation of HCO/sub 2//sup -/ by ((bpy)/sub 2/(py)Ru/sup III/(OH))/sup 2 +/ appears to occur by outer-sphere electron transfer.

• Research Organization: Univ. of North Carolina, Chapel Hill
• OSTI ID: 5582913
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 108:14; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400302* -- Organic Chemistry-- Isotope Effects-- (-1987)
400500 -- Photochemistry
AZINES
BIPYRIDINES
CARBOXYLIC ACIDS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPLEXES
DATA
DEUTERIUM
ELEMENTS
EXPERIMENTAL DATA
FORMIC ACID
HETEROCYCLIC COMPOUNDS
HYDROGEN
HYDROGEN ISOTOPES
INFORMATION
ISOTOPE EFFECTS
ISOTOPES
KINETICS
LIGHT NUCLEI
MEDIUM TEMPERATURE
MONOCARBOXYLIC ACIDS
NONMETALS
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIDATION
PYRIDINES
REACTION KINETICS
RUTHENIUM COMPLEXES
STABLE ISOTOPES
TRANSITION ELEMENT COMPLEXES