Oxidative and electrophilic pathways in the reactions of organochromium(III) complexes with nitrous acid and tris(2,2'-bipyridyl) ruthenium(III). [Organochromium(III) complexes]

Technical Report · Sun Jun 01 04:00:00 EDT 1986

OSTI ID:5497247

Melton, J D

The kinetics and mechanisms of the reactions of nitrous acid with pentaaquoorganochromium(III) complexes were studied. The rate constants for the aliphatic organochromium complexes can be correlated using a linear free energy correlation which implies a common transition state for these reactions. The lack of steric effects for the reactions of the alkylchromium complexes, and the detection of Cr/sup 2 +/ as an intermediate in the reactions of the ..cap alpha..-hydroxy- and ..cap alpha..-alkoxyalkylchromium complexes suggests that these complexes react with HONO by an electron transfer mechanism. In contrast, aralkylchromium(III) complexes react with nitrous acid by an electrophilic mechanism as indicated by the products and correlations of the rate constants with other electrophilic reactions in the literature. 78 refs., 13 figs., 28 tabs.

• Research Organization: Ames Lab., IA (USA)
• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 5497247
• Report Number(s): IS-T-1193; ON: DE86012674
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHROMIUM COMPLEXES
COMPLEXES
ELECTRON TRANSFER
HYDROGEN COMPOUNDS
INORGANIC ACIDS
KINETICS
NITROUS ACID
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXIDATION
REACTION KINETICS
REFRACTORY METAL COMPOUNDS
RUTHENIUM COMPOUNDS
SPECTROPHOTOMETRY
STEREOCHEMISTRY
STOICHIOMETRY
TITRATION
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS