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Cited by 58Synthesis and Properties of Aromatic CompoundsAdvanced Chemical Physics StudiesOrganic Chemistry Cycloaddition Reactions

The DOI matches its Crossref record; 100 of the 101 references it cites were found in a registry or an index.

Why Cyclooctatetraene Is Highly Stabilized: The Importance of “Two-Way” (Double) Hyperconjugation

Wu, Judy I., Fernández, Israel, Mo, Yirong, Schleyer, Paul von Ragué·2012·Journal of Chemical Theory and Computation
DOI 10.1021/ct3000553
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Abstract

Despite its highly nonplanar geometry, the tub-shaped D2d cyclooctatetraene (COT) minimum is far from being an unconjugated polyene model devoid of important π interactions. The warped skeleton of D2d COT results in the large stabilization (41.1 kcal/mol) revealed by its isodesmic bond separation energy (BSE). This originates largely from the "two-way" hyperconjugation, back and forth across the C-C single bonds, between the CC/CH σ(σ*) and the C═C (π*)π orbitals. These hyperconjugative effects compensate for the substantial, but not complete, loss of π conjugation upon ring puckering. C-C single bond rotation of 1,3-butadiene involves a similar interplay between π conjugation and "two-way" double hyperconjugation and serves as a simple model for the inversion of D2d to D4h COT. The perpendicular rotational transition states of many other systems, e.g., the allyl cation, styrene, biphenyl, and ethene, are stabilized similarly by "two-way" hyperconjugation.

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Crossref · 10.1021/ct3000553

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  • The tub-shaped form of cyclooctatetraene is stabilized by hyperconjugation.

    “Also, the tub-shaped form is stabilized by hyperconjugation [182].”

    From Aromaticity and Antiaromaticity: How to Define Them (2025) · cites this paper as [182]

  • The conjugative π→π* stabilization of cyclooctatetraene is reduced by 33.6 kcal/mol, as estimated by NBO del analysis.

    “while the conjugative π → π* stabilization is reduced by 33.6 kcal/mol, as estimated by NBO del analysis [182].”

    From Aromaticity and Antiaromaticity: How to Define Them (2025) · cites this paper as [182]

Citations

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1 of the 101 references couldn’t be matched to a known paper.

Research works printed but not linked: 13

  1. Raphael R. A., 1959, Nonbenzenoid Aromatic Compounds, 465
  2. bSnyder, J. P.InNonbenzenoid Aromatics;Academic Press:New York, 1969; Vol.1, p29.
  3. Nevins N., 1996, J. Comput. Chem., 17, 695
  4. Pauling, L.InThe Nature of the Chemical Bond,3rd ed.Cornell University Press:Ithaca, NY, 1960; p196.
  5. Cohen N., 1993, Chem. Rev., 93, 2419, 10.1021/cr00023a005 · DOI
  6. Claus K. H., 1988, Acta Crystallogr., 44, 1632
  7. Mo Y., 2010, Nature, 2, 666
  8. Angew. Chem., Int. Ed. 2004, 43, 1986–1990.
  9. Song L., 2003, XMVB: Ab initio Non-orthogonal Valence Bond Program
  10. Mo Y., 2011, Phys. Chem. Chem. Phys., 13, 6760, 10.1039/c0cp02206c · DOI
  11. Glendening X., 2003, NBO 5
  12. Frisch M. J., 2004, Gaussian 03
  13. Xi H. W., 2008, J. Phys. Chem. A, 112, 13066, 10.1021/jp803837h · DOI

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Metadata

Authors
Wu, J. I., Fernández, I., Mo, Y., & Schleyer, P. V. R.
Affiliations
  • University of Georgia (US)
  • Universidad Complutense de Madrid (ES)
  • Western Michigan University (US)
Corresponding author
Schleyer, Paul von Ragué
ORCID
Venue
Journal of Chemical Theory and Computation
Publisher
American Chemical Society (ACS)
Published
2012-03-15
Volume
8
Issue
4
Pages
1280-1287
ISSN
  • 1549-9618 (ISSN-L)
  • 1549-9626
DOI
10.1021/ct3000553
OpenAlex
W2316548484
Cited by
58
References
101
Citations by year
2026: 3 · 2025: 2 · 2024: 4 · 2023: 1 · 2022: 5 · 2021: 3 · 2020: 6 · 2019: 6 · 2018: 4 · 2017: 2 · 2016: 4 · 2015: 3 · 2014: 5 · 2013: 6 · 2012: 4
FWCI
2.65
Type
journal article
Language
en
Open access
closed
Locations
  • Journal of Chemical Theory and Computation (publishedVersion)
  • PubMed (publishedVersion)
Topics
  • Physical Sciences › Chemistry › Organic Chemistry › Synthesis and Properties of Aromatic Compounds
  • Physical Sciences › Physics and Astronomy › Atomic and Molecular Physics, and Optics › Advanced Chemical Physics Studies
  • Physical Sciences › Chemistry › Organic Chemistry › Organic Chemistry Cycloaddition Reactions
Keywords
cyclooctatetraene, ring puckering, π-conjugation, 1,3-butadiene, allyl cations, styrene, biphenyl, ethylene

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