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The mechanism of the ozonolysis on the surface of C70 fullerene: the electron localizability indicator study

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Abstract

The formation of C70O from C70O3 monomolozonide is a three-step process with the isomer dependent last step leading either to c,c-C70O epoxide or d,d-C70O oxidoannulene. The process involves the open intermediate (first O–O then Cc–Cc/Cd–Cd bonds broken), oxidoannulene-like structure intermediate (new Cc–O/Cd–O bond formed) and finally the oxide product. On the formation of c,c-C70O isomer, the final release of O2 is followed by the restoration of Cc–Cc bond, which stabilizes the product. Neither Cd–Cd bond is restored nor the total energy essentially lowered upon d,d-C70O formation. At all steps of the studied process, the four CC bonds adjacent to Cc–Cc or Cd–Cd bond, respectively, play a crucial role donating or withdrawing the necessary electron density. C70(O)O2 products, with O2 bridging one of the bonds adjacent to the parent Cc–Cc/Cd–Cd one, may compete with the oxide products. The OO bond in such structures is weak as suggested by its low electron population. For both c,c-C70O3 and d,d-C70O3, the shape of the potential energy surfaces (0 K) and the related, reported earlier, room temperature–free energy surfaces differ.

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Acknowledgments

The authors would like to express personal gratitude to professor Zdzisław Latajka, a noble man and a supervisor of their PhD theses, for fruitful long-standing collaboration.

Funding

A grant of computer time from the Wrocław Center for Networking and Supercomputing (WCSS) is gratefully acknowledged. A.B. would like to thank the Ministry of Science and Higher Education, Republic of Poland, for supporting this work under the grant no. N N204 280738.

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  1. Faculty of Chemistry, University of Wrocław, 14 F. Joliot-Curie, 50-383, Wrocław, Poland

    Andrzej Bil

  2. Wrocław, Poland

    Krzysztof Mierzwicki

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Correspondence to Andrzej Bil.

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This paper is dedicated to Professor Zdzislaw Latajka, on occasion of his 70th birthday in recognition on his vital research contributions.

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This paper belongs to the Topical Collection Zdzislaw Latajka 70th Birthday Festschrift

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Figs. S1–S20 and Cartesian coordinates of the relevant stationary structures are available as Electronic supplementary material as well as extended discussion and additional comments concerning the bonds evolution along the reaction paths studied in the main body of the paper. (DOCX 5823 kb)

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Bil, A., Mierzwicki, K. The mechanism of the ozonolysis on the surface of C70 fullerene: the electron localizability indicator study. J Mol Model 26, 73 (2020). https://doi.org/10.1007/s00894-020-4333-8

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