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A mechanistic investigation on the formation and rearrangement of silaspiropentane: A theoretical study

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Abstract

The formation of silaspiropentane from addition of singlet silacyclopropylidene 1 and silacyclopropylidenoid 8 to ethylene has been investigated separately at the B3LYP, X3LYP, WB97XD, and M05–2X theories using the 6–31+G(d,p) basis set. The silacycloproylidenoid addition follows a stepwise route. In contrast, a concerted mechanism occurs for silacyclopropylidene addition. Moreover, the intramolecular rearrangements of silaspiropentane 9 to methylenesilacyclobutane 11 and 2-silaallene + ethylene 12 have been studied extensively. The required energy barrier for the isomerization of 9 to 10 was determined to be 44.0 kcal mol−1 at the B3LYP/6–31+G(d,p) level. After formation of 10, the rearrangement to methylenesilacyclobutane 12 is highly exergonic by −15.9 kcal mol−1, which makes this reaction promising. However, the conversion of 9 to 11 is calculated to be quite endergonic, by 26.5 kcal mol−1.

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Acknowledgments

Financial support by the Aksaray University (BAP2016–024) is gratefully acknowledged. We are very grateful to the reviewers for valuable comments that improved our manuscript.

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Authors and Affiliations

  1. Department of Chemistry, Faculty of Arts and Sciences, University of Aksaray, Aksaray, Turkey

    Cem Burak Yildiz

  2. Department of Chemistry, Laboratory of Computational Chemistry, University of Balikesir, TR–10145, Balikesir, Turkey

    Akin Azizoglu

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  1. Cem Burak Yildiz
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  2. Akin Azizoglu
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Correspondence to Cem Burak Yildiz.

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Yildiz, C.B., Azizoglu, A. A mechanistic investigation on the formation and rearrangement of silaspiropentane: A theoretical study. J Mol Model 22, 158 (2016). https://doi.org/10.1007/s00894-016-3016-y

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