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Electronic structure and decomposition reaction mechanism of cyclopropenone, phenylcylopropenone and their sulfur analogues: a theoretical study

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Abstract

The electronic structure, the origin of the extraordinary stability and the reaction mechanisms of the decomposition reaction of the three-membered ring cyclopropenone (IO), its phenyl derivative (IIO) and its sulfur analogues (IS and IIS) have been investigated at the B3LYP/6-311 + G** level of theory. All critical points on the reaction surface, reactants, transition states and intermediates were determined. Reaction rate constants and half-lives have been computed. Natural bond orbital (NBO) analysis has been used to investigate the type and extent of interaction in the studied species. Results indicate that the decomposition reaction occurs via a stepwise mechanism, with the formation of a short-lived intermediate. The characters of the intermediates for the decomposition of IIO and IIS are different. In case of IIO decomposition, the intermediate structure is of prevailing zwitterionic character, whereas that for the decomposition of IIS is of prevailing carbene character. Solvent effects are computed, analyzed and discussed.

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Acknowledgments

This Project was funded by the Deanship of Scientific Research (DSR) King Abdulaziz University, Jeddah, under grant no. D19-130-/1432. The authors, therefore, acknowledge with thanks DSR support for Scientific Research.

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Authors and Affiliations

  1. Chemistry Department, Faculty of Science, King Abdulaziz University, Jeddah, Saudi Arabia

    Shabaan A. K. Elroby, Saadullah G. Aziz & Rifaat Hilal

  2. Chemistry Department, Faculty of Science, Beni-Suief University, Beni-Suief, Egypt

    Shabaan A. K. Elroby

  3. Chemistry Department, Faculty of Science, Cairo University, Giza, Egypt

    Rifaat Hilal

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  1. Shabaan A. K. Elroby
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  2. Saadullah G. Aziz
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  3. Rifaat Hilal
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Correspondence to Rifaat Hilal.

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Elroby, S.A.K., Aziz, S.G. & Hilal, R. Electronic structure and decomposition reaction mechanism of cyclopropenone, phenylcylopropenone and their sulfur analogues: a theoretical study. J Mol Model 19, 1339–1353 (2013). https://doi.org/10.1007/s00894-012-1669-8

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  • DOI: https://doi.org/10.1007/s00894-012-1669-8

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