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Molecular structure and decomposition mechanism of peracetic acid esters AcOOR (R = Me, But)

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Abstract

The molecular structure and conformational mobility of methyl and tert-butyl esters of peracetic acid AcOOR (R = Me (1), But (2)) were studied by the ab initio MP4(SDQ)//MP2(FC)/6-31G(d,p) method and density functional B3LYP/6-31G(d,p) approach. The B3LYP calculated equilibrium conformations of the molecules are characterized by the C-O-O-C torsion angles of 93.6° (1) and 117.0° (2). Structural features of the molecules under study and a distortion of tetrahedral bond configuration at the Cα atom were explained using the natural bonding orbital approach. The standard enthalpies of formation of AcOOMe (−328.5 kJ mol−1) and AcOOBut (−440.4 kJ mol−1) were determined using the G2 and G2(MP2) computational schemes and the isodesmic reaction approach. The transition state of AcOOMe decomposition into AcOOH and formaldehyde was calculated (E a = 122.8 kJ mol−1). The thermal effects of homolytic decomposition of the peroxy esters following a concerted mechanism (Me· + CO2 + ·OR) and simple homolysis of the peroxide bond (AcO· + ·OR) were found to be 97.5±0.3 and 155.1±0.3 kJ mol−1, respectively. At temperatures below 400 K, the most probable decomposition mechanism of peroxy esters 1 and 2 involves simple homolysis of the O-O bond.

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Authors and Affiliations

  1. Bashkir State University, 32 ul. Frunze, 450074, Ufa, Russian Federation

    S. L. Khursan

  2. N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 4 ul. Kosygina, 119991, Moscow, Russian Federation

    V. L. Antonovsky

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  1. S. L. Khursan
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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2021–2027, October, 2004.

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Khursan, S.L., Antonovsky, V.L. Molecular structure and decomposition mechanism of peracetic acid esters AcOOR (R = Me, But). Russ Chem Bull 53, 2109–2116 (2004). https://doi.org/10.1007/s11172-005-0081-2

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