Gas Phase Structures of Peroxides: Experiments and Computational Problems

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Abstract
Gas‐phase structures of several organic and inorganic peroxides X‐O‐O‐X and X‐O‐O‐X′, which have been determined experimentally by gas electron diffraction and/or microwave spectroscopy, are discussed. The OO bond length in these peroxides varies from 1.481(8) Å in Me3SiOOSiMe3 to 1.214(2) Å in FOOF and the dihedral angle ϕ(XO‐OX) between 0° in HC(O)O‐OH and near 180° in ButO‐OBut. Some of the peroxides cause problems for quantum chemistry, since several computational methods fail to reproduce the experimental structures. Extreme examples are MeO‐OMe and FO‐OF. In the case of MeO‐OMe only about half of the more than 100 computational methods reported in the literature reproduce the experimentally determined double‐minimum shape of the torsional potential around the OO bond correctly. For FO‐OF only a small number of close to 200 computational methods reproduce the OO and OF bond lengths better than ±0.02 Å.

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