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A DFT investigation of the retro-ene reactions of β-hydroxyacetylenes: concerted or stepwise mechanism

  • Raakhi GuptaEmail author
  • R. K. Bansal
Original Research
  • 4 Downloads

Abstract

The retro-ene reactions of β-hydroxyacetylene and its 10 derivatives have been investigated theoretically at the B3LYP/6-31+G(d) level. The reactions are found to proceed through asynchronous concerted transition states. The thermodynamic data reveal that the reactions are exergonic with increase in the standard entropy. However, due to high values of the activation Gibbs free energy (∆G#) and negative values of the activation entropy (∆S#), reactions occur at elevated temperatures. The substituent groups in general do not have pronounced effect on the activation enthalpies, except the phenyl group in which case, it is lowered. The concerted versus stepwise mechanism has been investigated by complete active space-self consistent field (CASSCF) calculations also.

Keywords

Retro-ene reaction β-Hydroxyacetylenes Concerted versus stepwise mechanism DFT calculations CASSCF calculations 

Notes

Acknowledgements

Authors thank the authorities of the IIS (Deemed to be a University), Jaipur (India) for providing necessary facilities.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

11224_2019_1410_MOESM1_ESM.docx (3.4 mb)
ESM 1 (DOCX 3479 kb)

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Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Department of Chemistry IIS (Deemed to be University)JaipurIndia

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