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Unraveling the reaction pathways of cyclotrisilenes: a computational analysis

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Abstract

Cyclotrisilenes can pursue four types of reaction pathways with unsaturated substrates: π-addition, σ-insertion, exocyclic σ-insertion, and ring-opening reactions. A computational investigation of all these reaction pathways of 1,2,3,3-tetramethyl cyclotrisilene c-Si3Me4 (I) and 1,2-bis(trimethylsilyl)-3,3-dimethyl cyclotrisilene c-Si3Me2(SiMe3)2 (II) with phenylacetylene (R1) and benzaldehyde (R2) is carried out. The reaction pathways are found to be significantly influenced by the substituents attached to the cyclotrisilene ring. Both the π-addition and the σ-insertion reactions proceed with moderate activation energy and high exoergicity, and the electronic nature of the functional group is crucial in deciding the favorable pathway. The exocyclic σ-insertion reactions are found to possess a huge energy barrier, irrespective of the steric and electronic nature of cyclotrisilenes and the substrates. While the course of the reaction and the viability of the ring-opening reaction with phenylacetylene are impacted by the nature of cyclotrisilene, the ring-opening reactions of I and II with benzaldehyde are both highly endoergic.

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Acknowledgements

The authors are grateful to Rashtriya Uchchatar Shiksha Abhiyan (RUSA) and University Grants Commission (UGC) for the financial support. AK thanks Kerala State Council for Science, Technology and Environment (KSCSTE), for a fellowship.

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  1. Department of Chemistry, St. Joseph’s College (Autonomous) Devagiri, Calicut, Kerala, Affiliated to the University of Calicut, Calicut, Kerala, India

    Amrutha Kizhuvedath, Jose John Mallikasseri & Jomon Mathew

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Major part of the work has been done by A. K. and J. J. M. J. M. wrote the main manuscript. All authors reviewed the manuscript.

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Correspondence to Jomon Mathew.

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Kizhuvedath, A., Mallikasseri, J.J. & Mathew, J. Unraveling the reaction pathways of cyclotrisilenes: a computational analysis. Theor Chem Acc 143, 23 (2024). https://doi.org/10.1007/s00214-024-03099-9

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