The kinetic isotopic effect, bridge ligand, and mechanisms of oxidation of alkanes in solutions

Journal Article · Fri Oct 01 00:00:00 EDT 1982 · Dokl. Phys. Chem. (Engl. Transl.); (United States)

OSTI ID:6130494

Rudakov, E S

The purpose of this article was to call attention to a new and striking fact: the kinetic isotopic effect of hydrogen (KIE) in oxidative homolysis, in a first approximation, is independent of the central atom-oxidizing agent M/sup n/ and is determined exclusively by the bridge ligand, which is a quantitative criterion for the selection of the bridge. Most of the data were obtained recently in a study of the first step of the oxidation of alkanes in sulfuric acid and aqueous media by reagents which, as has been suggested, include sulfate (OSO/sub 2/O-) or oxo (O=) bridges. The structures of the reagents were selected considering data on the kinetics, selectivity, and KIE. For the reactions of RH with CF/sub 3/-COOH, HOCl(Cl/sub 2/ + H/sub 2/O), H/sub 2/SO/sub 5/ (H/sub 2/O/sub 2/-90% H/sub 2/SO/sub 4/) and HNO/sub 3/-Pt/sup IV/-Cl/sup -/-H/sub 2/O, structures with OH bridges were assumed. The values of the KIE are the same for tert- and sec-C-H bonds; the reproducibility is usually within +/- 15%.

• Research Organization: Academy of Sciences of the Ukranian, Donetsk, USSR
• OSTI ID: 6130494
• Journal Information: Dokl. Phys. Chem. (Engl. Transl.); (United States), Vol. 263:4-6; Other Information: Translated from Dokl. Akad. Nauk SSSR; 263: No. 4, 942-945(Jan 1982)
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ALKANES
OXIDATION
DEUTERIUM
ISOTOPE EFFECTS
CHEMICAL REACTION KINETICS
HYDROGEN
CHEMICAL REACTIONS
ELEMENTS
HYDROCARBONS
HYDROGEN ISOTOPES
ISOTOPES
KINETICS
LIGHT NUCLEI
NONMETALS
NUCLEI
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
REACTION KINETICS
STABLE ISOTOPES
400302* - Organic Chemistry- Isotope Effects- (-1987)