title: Gold nanoparticle-initiated free radical oxidations and halogen abstractions.
abstract: We report on the use of EPR spectroscopy and spin trapping technique to detect free radical intermediates formed in the presence of gold nanoparticles. Phosphine- and amine-protected gold nanoparticles were found to initiate air oxidation of organic substrates containing active hydrogen atoms, such as amines and phosphine oxides. Nanoparticles protected by stronger bound ligands (e.g., thiols) were inactive in these reactions. We also found that gold nanoparticles are able to abstract a halogen atom from the halogenated compounds, presumably due to the high affinity of gold metal for halogens. Reaction of Au nanoparticles with chloroform showed an unusual inverse isotope effect. The trichloromethyl spin adduct was observed when Au nanoparticles were mixed with CDCl(3) but not with CHCl(3). This unexpected behaviour suggests that C-H bond breaking is not the rate-determining step in Au-initiated hydrogen abstraction.
authors.affiliation: Department of Chemistry, University of York, Heslington, York, UK YO10 5DD.
authors.forename: Petre
authors.initials: P
authors.lastname: Ionita
authors.forename: Marco
authors.initials: M
authors.lastname: Conte
authors.forename: Bruce C
authors.initials: BC
authors.lastname: Gilbert
authors.forename: Victor
authors.initials: V
authors.lastname: Chechik