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The [2 + 2 + 2] mechanisms of trimerization of three ethynes and monosilaethylenes

Homologous concerted mechanism and polarized one-step mechanism

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Abstract

The mechanisms of [2 + 2 + 2] reactions of three ethynes and monosilaethylenes to form benzene and 1,3,5-trisilacyclohexane were studied by ab initio MO methods. The reaction mechanisms were analyzed by configuration interaction/localized molecular orbital/CASSCF calculations. Although the [2 + 2 + 2] reaction of ethyne is typically “homologous” concerted, that of monosilaethylene is polarized (ionic-cyclic) one-step reaction. In addition, the aromaticity along the intrinsic reaction coordinate pathway was studied using the index of deviation from aromaticity. Although the transition state of trimerization of ethyne does not have an aromatic nature for the σ- and π-bonds formation system, the crossing point of the σ-bond formation and π-bond breaking shows an aromatic nature.

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Acknowledgment

The present research is supported by a Grant-in-Aid for Scientific Research from the Ministry of Education Science and Culture of Japan. The computer time was made available by the Computer Center of the Institute for Molecular Science.

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Authors and Affiliations

  1. Department of Chemistry, Faculty of Engineering Gifu University, Yanagido, Gifu, 501-1193, Japan

    Shogo Sakai & Keitaro Taketa

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  1. Shogo Sakai
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  2. Keitaro Taketa
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Correspondence to Shogo Sakai.

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Dedicated to Professor Akira Imamura on the occasion of his 77th birthday and published as part of the Imamura Festschrift Issue.

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Sakai, S., Taketa, K. The [2 + 2 + 2] mechanisms of trimerization of three ethynes and monosilaethylenes. Theor Chem Acc 130, 901–907 (2011). https://doi.org/10.1007/s00214-011-0971-3

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  • DOI: https://doi.org/10.1007/s00214-011-0971-3

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