title: Dissociative electron attachment to triflates.
abstract: Gas phase studies of dissociative electron attachment to simple alkyl (CF(3)SO(3)CH(3)) and aryl (C(6)H(5)SO(3)CF(3) and CF(3)SO(3)C(6)H(4)CH(3)) triflates, model molecules of nonionic photoacid generators for modern lithographic applications, were performed. The fragmentation pathways under electron impact below 10 eV were identified by means of crossed electron-molecular beam mass spectrometry. Major dissociation channels involved C-O, S-O, or C-S bond scissions in the triflate moiety leading to the formation of triflate (OTf(-)), triflyl (Tf(-)), or sulfonate (RSO(3)(-)) anions, respectively. A resonance leading to C-O bond breakage and OTf(-) formation in alkyl triflates occurred at electron energies about 0.5 eV lower than the corresponding resonance in aryl triflates. A resonance leading to S-O bond breakage and Tf(-) formation in aryl triflates occurred surprisingly at the same electron energies as C-O bond breakage. In case of alkyl triflates S-O bond breakage required 1.4 eV higher electron energies to occur and proceeded with substantially lower yields than in aryl triflates. C-S bond scission occurred for all presently studied triflates at energies close to 3 eV.
authors.affiliation: Radiation Laboratory and Department of Physics, University of Notre Dame, Notre Dame, Indiana 46556, USA. sptasins@nd.edu
authors.forename: Sylwia
authors.initials: S
authors.lastname: Ptasińska
authors.forename: David
authors.initials: D
authors.lastname: Gschliesser
authors.forename: Peter
authors.initials: P
authors.lastname: Bartl
authors.forename: Ireneusz
authors.initials: I
authors.lastname: Janik
authors.forename: Paul
authors.initials: P
authors.lastname: Scheier
authors.forename: Stephan
authors.initials: S
authors.lastname: Denifl
mesh_terms: D000838:Anions / Q000737:chemistry; D004583:Electrons; D013058:Mass Spectrometry; D008698:Mesylates / Q000737:chemistry*
chemical_list: D000838:Anions; D008698:Mesylates; C078465:methyl triflate