Understanding kinetic solvent effects on hydrogen abstraction reactions from carbon by the cumyloxyl radical.
A kinetic study of the hydrogen abstraction reactions from tetrahydrofuran (THF) and cyclohexane (CHX) by the cumyloxyl radical was carried out in different solvents. With THF, a 4.5-fold decrease in rate constant (k(H)) was observed on going from isooctane to 2,2,2-trifluoroethanol. An opposite behavior was observed with CHX, where k(H) increased by a factor 4 on going from isooctane to 2,2,2-trifluoroethanol. The important role of substrate structure and of the solvent  hydrogen bond donor ability is discussed.
Dipartimento di Scienze e Tecnologie Chimiche, Università Tor Vergata, Via della Ricerca Scientifica, 1 I-00133 Rome, Italy.
Massimo
M
Bietti
Roberto
R
Martella
Michela
M
Salamone
D002244:Carbon / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D007700:Kinetics; D015394:Molecular Structure; D017382:Reactive Oxygen Species / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry
D017382:Reactive Oxygen Species; D012997:Solvents; D002244:Carbon; D006859:Hydrogen