title: Diffusion controlled hydrogen atom abstraction from tertiary amines by the benzyloxyl radical. The importance of C-H/N hydrogen bonding.
abstract: The rate constants for H-atom abstraction (k(H)) from 1,4-cyclohexadiene (CHD), triethylamine (TEA), triisobutylamine (TIBA), and DABCO by the cumyloxyl (CumO(•)) and benzyloxyl (BnO(•)) radicals were measured. Comparable k(H) values for the two radicals were obtained in their reactions with CHD and TIBA whereas large increases in k(H) for TEA and DABCO were found on going from CumO(•) to BnO(•). These differences are attributed to the rate-determining formation of BnO(•) C-H/amine N lone-pair H-bonded complexes.
authors.affiliation: Dipartimento di Scienze e Tecnologie Chimiche, Università Tor Vergata, Via della Ricerca Scientifica, 1 I-00133 Rome, Italy.
authors.forename: Michela
authors.initials: M
authors.lastname: Salamone
authors.forename: Gloria
authors.initials: G
authors.lastname: Anastasi
authors.forename: Massimo
authors.initials: M
authors.lastname: Bietti
authors.forename: Gino A
authors.initials: GA
authors.lastname: DiLabio
mesh_terms: D000588:Amines / Q000737:chemistry*; D001555:Benzene Derivatives / Q000737:chemistry*; D053138:Cyclohexenes / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D006860:Hydrogen Bonding; D008956:Models, Chemical; D015394:Molecular Structure; D010879:Piperazines / Q000737:chemistry*
chemical_list: D000588:Amines; D001555:Benzene Derivatives; D053138:Cyclohexenes; D010879:Piperazines; C048401:1,4-cyclohexadiene; D006859:Hydrogen; C007306:triethylenediamine