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Substituent Effects on Torsional Strain in Cyclopentene Derivatives: A Computational Study

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Download Hi-Res ImageDownload to MS-PowerPointCite This:J. Phys. Chem. A 2023, 127, 23, 5005-5017
    A: Structure, Spectroscopy, and Reactivity of Molecules and Clusters

    Substituent Effects on Torsional Strain in Cyclopentene Derivatives: A Computational Study
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    • Brianna M. Coia
      Brianna M. Coia
      Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, United States
      More by Brianna M. Coia
    • Luke A. Hudson
      Luke A. Hudson
      Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, United States
      More by Luke A. Hudson
    • August J. Specht III
      August J. Specht, III
      Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, United States
      More by August J. Specht, III
    • Justin G. Kennemur*
      Justin G. Kennemur
      Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, United States
      *Email: [email protected]
      More by Justin G. Kennemur
      Orcidhttps://orcid.org/0000-0002-2322-0386
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    The Journal of Physical Chemistry A

    Cite this: J. Phys. Chem. A 2023, 127, 23, 5005–5017
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    https://doi.org/10.1021/acs.jpca.3c02267
    Published June 6, 2023
    Copyright © 2023 American Chemical Society
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    Abstract

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    Density functional theory calculations were used to create a library of ring strain energies (RSEs) for 73 cyclopentene derivatives with potential use as monomers for ring-opening metathesis polymerization (ROMP). An overarching goal was to probe how substituent choice may influence torsional strain, which is the driving force for ROMP and one of the most understudied types of RSEs. Potential trends investigated include substituent location, size, electronegativity, hybridization, and steric bulk. Using traditional and recently developed homodesmotic equations, our results show that the size and substitution (bulk) of the atom directly bonded to the ring have the greatest influence on torsional RSE. A complex interplay between bond length, bond angle, and dihedral angle dictates the relative eclipsed conformations between the substituent and its neighboring hydrogens and was found to be responsible for the notable differences in RSEs. Furthermore, substituents placed on the homoallylic position resulted in higher RSEs than the same substituent placed on the allylic position due to increased eclipsing interactions. Different levels of theory were also assessed, and it was determined that consideration of electron correlation in calculations increased RSEs by ∼2–5 kcal mol–1. Further increasing the level of theory did not significantly change RSEs, indicating that the increased computational cost and time may not be necessary for improved accuracy.

    Copyright © 2023 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpca.3c02267.

    • RSE calculations, H2 substituent location vs RSE, H2 size and electronegativity vs RSE, substituent hybridization, steric bulk descriptors, and structure coordinates (PDF)

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    The Journal of Physical Chemistry A

    Cite this: J. Phys. Chem. A 2023, 127, 23, 5005–5017
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpca.3c02267
    Published June 6, 2023
    Copyright © 2023 American Chemical Society
    Request reuse permissions

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