Perfluoromethyl Fluorocarbonyl Peroxide, CF3OOC(O)F: Structure, Conformations, and Vibrational Spectra Studied by Experimental and Theoretical Methods
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- 作者：Frank Trautner ; Khodayar Gholivand ; Plá ; cido Garcí ; a ; Helge Willner ; Mauricio F. Erben ; Carlos O. Della Vé ; dova ; and Heinz Oberhammer
- 刊名：Inorganic Chemistry
- 出版年：2003
- 出版时间：May 5, 2003
- 年：2003
- 卷：42
- 期：9
- 页码：3079 - 3085
- 全文大小：118K
- 年卷期：v.42,no.9(May 5, 2003)
- ISSN：1520-510X
文摘
The conformational properties and the geometric structure of perfluoromethyl fluorocarbonyl peroxide, CF3OOC(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 
H
= Hanti - Hsyn = 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) Å) is withinthe experimental uncertainties equal to those in related symmetrically substituted peroxides CF3OOCF3 andFC(O)OOC(O)F (1.419(20) and 1.419(9) Å, respectively), and the dihedral angle 
(COOC) (111(5)) is intermediatebetween the values in these two compounds (123(4) and 83.5(14), respectively).
H = Hanti - Hsyn = 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) Å) is withinthe experimental uncertainties equal to those in related symmetrically substituted peroxides CF3OOCF3 andFC(O)OOC(O)F (1.419(20) and 1.419(9) Å, respectively), and the dihedral angle (COOC) (111(5)) is intermediatebetween the values in these two compounds (123(4) and 83.5(14), respectively).