title: Negative-ion photoelectron spectroscopy, gas-phase acidity, and thermochemistry of the peroxyl radicals CH(3)OO and CH(3)CH(2)OO.
abstract: Methyl, methyl-d(3), and ethyl hydroperoxide anions (CH(3)OO(-), CD(3)OO(-), and CH(3)CH(2)OO(-)) have been prepared by deprotonation of their respective hydroperoxides in a stream of helium buffer gas. Photodetachment with 364 nm (3.408 eV) radiation was used to measure the adiabatic electron affinities: EA[CH(3)OO, X(2)A' '] = 1.161 +/- 0.005 eV, EA[CD(3)OO, X(2)A' '] = 1.154 +/- 0.004 eV, and EA[CH(3)CH(2)OO, X(2)A' '] = 1.186 +/- 0.004 eV. The photoelectron spectra yield values for the term energies: Delta E(X(2)A' '-A (2)A')[CH(3)OO] = 0.914 +/- 0.005 eV, Delta E(X(2)A' '-A (2)A')[CD(3)OO] = 0.913 +/- 0.004 eV, and Delta E(X(2)A' '-A (2)A')[CH(3)CH(2)OO] = 0.938 +/- 0.004 eV. A localized RO-O stretching mode was observed near 1100 cm(-1) for the ground state of all three radicals, and low-frequency R-O-O bending modes are also reported. Proton-transfer kinetics of the hydroperoxides have been measured in a tandem flowing afterglow-selected ion flow tube (FA-SIFT) to determine the gas-phase acidity of the parent hydroperoxides: Delta(acid)G(298)(CH(3)OOH) = 367.6 +/- 0.7 kcal mol(-1), Delta(acid)G(298)(CD(3)OOH) = 367.9 +/- 0.9 kcal mol(-1), and Delta(acid)G(298)(CH(3)CH(2)OOH) = 363.9 +/- 2.0 kcal mol(-1). From these acidities we have derived the enthalpies of deprotonation: Delta(acid)H(298)(CH(3)OOH) = 374.6 +/- 1.0 kcal mol(-1), Delta(acid)H(298)(CD(3)OOH) = 374.9 +/- 1.1 kcal mol(-1), and Delta(acid)H(298)(CH(3)CH(2)OOH) = 371.0 +/- 2.2 kcal mol(-1). Use of the negative-ion acidity/EA cycle provides the ROO-H bond enthalpies: DH(298)(CH(3)OO-H) = 87.8 +/- 1.0 kcal mol(-1), DH(298)(CD(3)OO-H) = 87.9 +/- 1.1 kcal mol(-1), and DH(298)(CH(3)CH(2)OO-H) = 84.8 +/- 2.2 kcal mol(-1). We review the thermochemistry of the peroxyl radicals, CH(3)OO and CH(3)CH(2)OO. Using experimental bond enthalpies, DH(298)(ROO-H), and CBS/APNO ab initio electronic structure calculations for the energies of the corresponding hydroperoxides, we derive the heats of formation of the peroxyl radicals. The "electron affinity/acidity/CBS" cycle yields Delta(f)H(298)[CH(3)OO] = 4.8 +/- 1.2 kcal mol(-1) and Delta(f)H(298)[CH(3)CH(2)OO] = -6.8 +/- 2.3 kcal mol(-1).
authors.affiliation: Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309-0215, USA.
authors.forename: S J
authors.initials: SJ
authors.lastname: Blanksby
authors.forename: T M
authors.initials: TM
authors.lastname: Ramond
authors.forename: G E
authors.initials: GE
authors.lastname: Davico
authors.forename: M R
authors.initials: MR
authors.lastname: Nimlos
authors.forename: S
authors.initials: S
authors.lastname: Kato
authors.forename: V M
authors.initials: VM
authors.lastname: Bierbaum
authors.forename: W C
authors.initials: WC
authors.lastname: Lineberger
authors.forename: G B
authors.initials: GB
authors.lastname: Ellison
authors.forename: M
authors.initials: M
authors.lastname: Okumura
mesh_terms: D000838:Anions / Q000737:chemistry*; D005609:Free Radicals / Q000737:chemistry; D013058:Mass Spectrometry / Q000379:methods*; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry*; D008956:Models, Chemical; D010545:Peroxides / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D000838:Anions; D005609:Free Radicals; D010545:Peroxides; C025577:ethyl hydroperoxide; C051224:methyl radical; C049375:perhydroxyl radical; D008697:Methane