EFFECT OF SPACE-ORIENTATION FACTORS ON KINETICS OF LOW-TEMPERATURE CARBENE REACTIONS

Citation
Ey. Davydov et al., EFFECT OF SPACE-ORIENTATION FACTORS ON KINETICS OF LOW-TEMPERATURE CARBENE REACTIONS, Journal of physical chemistry, 100(30), 1996, pp. 12403-12409
Citations number
24
Categorie Soggetti
Chemistry Physical
ISSN journal
00223654
Volume
100
Issue
30
Year of publication
1996
Pages
12403 - 12409
Database
ISI
SICI code
0022-3654(1996)100:30<12403:EOSFOK>2.0.ZU;2-U
Abstract
The character of nonexponential kinetics of the low-temperature decay of triplet carbenes in polymers has been given consideration. The temp erature dependencies of the decay rate and the kinetic isotope effect were found at 77-180 K. The controlling factor in the kinetic nonequiv alence of carbenes is the distribution of distances of the hydrogen at om tunneling from the matrix molecules. The effect of magnetic field o n the rate of the carbene decay has been seen at 77 K. On the basis of the magnetic dependence view, the mechanism of the carbene decay invo lving spin and chemical dynamics of intermediate short-lived radical p airs has been advanced, The nature of magnetic effect in polymers show s the configuration inhomogeneity of radical pairs.