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

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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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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Keywords

  • Silacyclopropylidenoid
  • Silacyclopropylidene
  • Silaspiropentane
  • Addition reaction
  • DFT