Reactions of bis(dimethylglyoximato)cobalt(II) complexes with tert-butyl hydroperoxide

Journal Article · Wed Sep 14 00:00:00 EDT 1983 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00161a029· OSTI ID:5709500

Espenson, J H; Melton, J D

Results show that the change in products and stoichiometry between aqueous solutions and benzene solvents arises from the effect of solvent on the rate constant for Beta-scission of the first radical intermediate, (C-H/sub 3/)/sub 3/CO. In benzene, the rate of the reaction is so slow that hydrogen atom abstraction occurs instead, leading to a second oxygen-centered radical, (CH/sub 3/)/sub 3/COO., and finally to the isolated product, (tert-butylperoxy)cobaloxime. The most extensive measurements were made by flash photolysis. Products were characterized by /sup 1/H NMR. 1 figure.

• Research Organization: Ames Lab., IA
• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 5709500
• Journal Information: Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 22:19; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400104 -- Spectral Procedures-- (-1987)
400201 -- Chemical & Physicochemical Properties
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400500 -- Photochemistry
ALKANES
AMINES
AQUEOUS SOLUTIONS
AROMATICS
BENZENE
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
COBALT COMPLEXES
COMPARATIVE EVALUATIONS
COMPLEXES
DATA
DISPERSIONS
EXPERIMENTAL DATA
HYDROCARBONS
HYDROXY COMPOUNDS
INFORMATION
KINETICS
MIXTURES
NMR SPECTRA
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC SOLVENTS
OXIMES
OXYGEN COMPOUNDS
PEROXIDES
PHOTOCHEMICAL REACTIONS
RADICALS
REACTION KINETICS
SOLUTIONS
SOLVENT PROPERTIES
SOLVENTS
SPECTRA
STOICHIOMETRY
STRUCTURAL CHEMICAL ANALYSIS
TRANSITION ELEMENT COMPLEXES
YIELDS