The low-energy unimolecular reaction rate constants for the gas phase, Ni+-mediated dissociation of the C-C sigma bond in acetone.
The time dependence of the gaseous unimolecular decomposition of the jet-cooled adduct ion, Ni+-OC(CH3)2, was monitored through selective detection of the Ni+CO fragment ion. Various resolved amounts of energy in the range 15600-18800 cm(-1) were supplied to initiate the dissociation reaction through absorption of laser photons by the title molecular complex. First-order rate constants, k(E), ranged from 113000 to 55000 s(-1) and decreased with decreasing amounts of internal excitation. The energy used to initiate the reaction is well below that required to fragment C-C sigma bonds and indicates the necessity of the Ni+ cation to induce bond activation and fragmentation. These measurements are carried out in a unique apparatus and represent the first direct kinetic study of such catalytic type reactions.
Castleberry
Vanessa A
VA
Department of Chemistry and Biochemistry, Baylor University, One Bear Place #97348, Waco, Texas 76798-7348, USA.
Dee
S Jason
SJ
Villarroel
Otsmar J
OJ
Laboren
Ivanna E
IE
Frey
Sarah E
SE
Bellert
Darrin J
DJ