title: Perfluoromethyl fluorocarbonyl peroxide, CF3OOC(O)F: structure, conformations, and vibrational spectra studied by experimental and theoretical methods.
abstract: The conformational properties and the geometric structure of perfluoromethyl fluorocarbonyl peroxide, CF(3)OOC(O)F, have been studied by matrix IR spectroscopy, gas electron diffraction, and quantum chemical calculations (HF, B3LYP, and MP2 methods with 6-311G* basis sets). Matrix IR spectra imply a mixture of syn and anti conformers (orientation of the C=O bond relative to the O-O bond) with DeltaH degrees = H(anti) degrees - H(syn) degrees = 2.16(22) kcal/mol. At room temperature, the contribution of the anti rotamer is about 3.0%. The O-O bond (1.422(15) A) is within the experimental uncertainties equal to those in related symmetrically substituted peroxides CF(3)OOCF(3) and FC(O)OOC(O)F (1.419(20) and 1.419(9) A, respectively), and the dihedral angle delta(COOC) (111(5) degrees ) is intermediate between the values in these two compounds (123(4) degrees and 83.5(14) degrees, respectively).
authors.affiliation: Institut für Physikalische und Theoretische Chemie, Universität Tübingen, D-72076 Tübingen, Germany.
authors.forename: Frank
authors.initials: F
authors.lastname: Trautner
authors.forename: Khodayar
authors.initials: K
authors.lastname: Gholivand
authors.forename: Plácido
authors.initials: P
authors.lastname: García
authors.forename: Helge
authors.initials: H
authors.lastname: Willner
authors.forename: Mauricio F
authors.initials: MF
authors.lastname: Erben
authors.forename: Carlos O
authors.initials: CO
authors.lastname: Della Védova
authors.forename: Heinz
authors.initials: H
authors.lastname: Oberhammer