Formation and decomposition of transient complexes with a copper-carbon /sigma/-bond in the reaction of copper(I) phenanthroline with aliphatic free radicals. A pulse radiolysis study
The oxidation of copper(I) phenanthroline by /center dot/CH/sub 2/CH/sub 2/OH and /center dot/CH/sub 2/C(CH/sub 3/)/sub 2/OH free radicals yields ethylene and 2-methylpropene, respectively. During this process transients with a copper-carbon /sigma/-bond have been observed with an absorbance similar to that of copper(I) phenanthroline in the visible region. Rate constants for the formation of these transients are estimated to be larger than 10/sup 10/ M/sup /minus/1/ s/sup /minus/1/. These intermediates decompose via a /beta/-hydroxyl elimination reaction with specific rate constants of (1.7 /plus minus/ 0.4) /times/ 10/sup 3/ and (1.1 /plus minus/0.3) /times/ 10/sup 4/ s/sup /minus/1/ for /center dot/CH/sub 2/C(CH/sub 3/)/sub 2/OH and /center dot/CH/sub 2/CH/sub 2/OH in the pH range 4-10, respectively. The mechanism of the decomposition is discussed, and a stability constant for the ligation of /center dot/CH/sub 2/C(CH/sub 3/)/sub 2/OH and /center dot/CH/sub 2/CH/sub 2/OH to the cuprous complex is estimated to be larger than 6 /times/ 10/sup 6/ M/sup /minus//. 28 refs., 5 figs., 3 tabs.
- Research Organization:
- Hebrew Univ., of Jerusalem (Israel)
- OSTI ID:
- 5775132
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 27:23; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400600* -- Radiation Chemistry
ALCOHOLS
ALKANES
AROMATICS
AZAARENES
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
COPPER COMPLEXES
DATA
DECOMPOSITION
ELECTRONS
ELEMENTARY PARTICLES
EXPERIMENTAL DATA
FERMIONS
HETEROCYCLIC COMPOUNDS
HYDROCARBONS
HYDROXY COMPOUNDS
INFORMATION
IRRADIATION
LEPTONS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHENANTHROLINES
PULSED IRRADIATION
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIOLYSIS
TRANSITION ELEMENT COMPLEXES