Angewandte Chemie International Edition
Explore this journal >
Communication

X-Ray Diffraction Evidence for a Cyclohexatriene Motif in the Molecular Structure of Tris(bicyclo[2.1.1]hexeno)benzene: Bond Alternation after the Refutation of the Mills–Nixon Theory†

Authors

  • Prof. Dr. Hans-Beat Bürgi,

    Corresponding author
    1. Laboratorium für Chemische und Mineralogische Kristallographie der Universität, CH-3012 Bern (Switzerland)
    • Laboratorium für Chemische und Mineralogische Kristallographie, der Universität, CH-3012 Bern (Switzerland)
    Search for more papers by this author

  • Dr. Kim K. Baldridge,

    1. San Diego Supercomputer Center, San Diego, CA (USA)
    Search for more papers by this author

  • Prof. Kenneth Hardcastle,

    1. Department of Chemistry, California State University-Northridge, Northridge, CA (USA)
    Search for more papers by this author

  • Natia L. Frank,

    1. Department of Chemistry, University of California-San Diego, La Jolla, CA 92093-0358 (USA). Telefax: Int. code + (619) 534-5383
    Search for more papers by this author

  • Dr. Peter Gantzel,

    1. Department of Chemistry, University of California-San Diego, La Jolla, CA 92093-0358 (USA). Telefax: Int. code + (619) 534-5383
    Search for more papers by this author

  • Prof. Jay S. Siegel,

    Corresponding author
    1. Department of Chemistry, University of California-San Diego, La Jolla, CA 92093-0358 (USA). Telefax: Int. code + (619) 534-5383
    • Department of Chemistry, University of California-San Diego, La Jolla, CA 92093-0358 (USA). Telefax: Int. code + (619) 534-5383
    Search for more papers by this author

  • Dr. Joseph Ziller

    1. Department of Chemistry, University of California-Irvine, Irvine, CA (USA)
    Search for more papers by this author
  • †

    This work was supported by the National Science Foundation (CHE-9307582, ASC-8902827), the Alfred P. Sloan Foundation (J. S. S), and the Schweizerischen Nationalfonds zur Förderung der wissenschaftlichen Forschung (H. B. B). The San Diego Supercomputer Center provided a grant for computing time.

Abstract

original image

Cyclohexatriene lost, cyclohexatriene regained! Recently the Mills–Nixon postulate concerning the structure of benzene derivatives was recognized to be invalid. A new view on strain-induced bond localization in benzene led to the design and synthesis of tris(bicyclo[2.1.1]hexeno)benzene (1), which shows significant distortion toward a cyclohexatriene geometry.

Continue reading full article

Ancillary

Article Information

DOI

10.1002/anie.199514541

Format Available

Full text: PDF

Copyright © 1995 by VCH Verlagsgesellschaft mbH, Germany

Request Permissions

Keywords

  • bond length alternation;
  • cyclohexatriene;
  • Mills–Nixon effect

Publication History

  • Issue online:
  • Version of record online:
  • Manuscript Received:

Related content

Articles related to the one you are viewing

Citing Literature

  • Number of times cited: 64
  1. 1Renana Gershoni-Poranne, Amnon Stanger, Magnetic criteria of aromaticity, Chem. Soc. Rev., 2015, 44, 18, 6597CrossRef
  2. 2Supriya Dey, Krishnayan Basuroy, N. Jayaraman, Solid state structure of p-bromo phenyl 4,5,7-tri-O-benzyl-β-d-glycero-d-talo-septanoside and an analysis of non-covalent interactions, Carbohydrate Research, 2015, 410, 9CrossRef
  3. 3Computational Organic Chemistry, 2014, 99CrossRef
  4. 4Alexandru T. Balaban, Alexander Greer, Joel F. Liebman, , 2014, 113, 111CrossRef
  5. 5Xiaoguang Bao, David A. Hrovat, Weston Thatcher Borden, Cooperative and competitive effects associated with Fe(CO)3binding to annelated benzenes, Chem. Sci., 2013, 4, 1, 516CrossRef
  6. 6Qi Song, Bing Wang, Ke Deng, Xinliang Feng, Manfred Wagner, Julian D. Gale, Klaus Müllen, Linjie Zhi, Graphenylene, a unique two-dimensional carbon network with nondelocalized cyclohexatriene units, J. Mater. Chem. C, 2013, 1, 1, 38CrossRef
  7. 7Matthias Müller, Cäcilia Maichle-Mössmer, Peter Sirsch, Holger F. Bettinger, Is There B[BOND]N Bond-Length Alternation in 1,2:3,4:5,6-Tris(biphenylylene)borazines?, ChemPlusChem, 2013, 78, 9, 988Wiley Online Library
  8. 8Orbital Interactions in Chemistry, 2013, 272CrossRef
  9. 9Ayorinde Hassan, Tandabany C. Dinadayalane, Sławomir J. Grabowski, Jerzy Leszczynski, Structural, energetic, spectroscopic and QTAIM analyses of cation–π interactions involving mono- and bi-cyclic ring fused benzene systems, Physical Chemistry Chemical Physics, 2013, 15, 48, 20839CrossRef
  10. 10Tandabany C. Dinadayalane, Ayorinde Hassan, Jerzy Leszczynski, A theoretical study of cation--π interactions: Li+, Na+, K+, Be2+, Mg2+ and Ca2+ complexation with mono- and bicyclic ring-fused benzene derivatives, Theoretical Chemistry Accounts, 2012, 131, 3CrossRef
  11. 11Fabrizio Fabris, Cristiano Zonta, Giuseppe Borsato, Ottorino De Lucchi, Benzocyclotrimers: From the Mills−Nixon Effect to Gas Hosting, Accounts of Chemical Research, 2011, 44, 6, 416CrossRef
  12. 12Xiaoguang Bao, David A. Hrovat, Weston Thatcher Borden, Cooperative effects in the annelation of benzene by multiple etheno groups, Collection of Czechoslovak Chemical Communications, 2011, 76, 5, 481CrossRef
  13. 13Piotr Cysewski, Influence of thermal vibrations on aromaticity of benzene, Physical Chemistry Chemical Physics, 2011, 13, 28, 12998CrossRef
  14. 14Kelling J. Donald, Matthew Bober, Predicting the Relative Stability of Simple versus ansa-Sandwich Systems Across Groups: Structure, Bonding, and (In)Stability in Tris(sandwich)benzene Complexes, Chemistry - A European Journal, 2011, 17, 6, 1936Wiley Online Library
  15. 15Xiaoguang Bao, David A. Hrovat, Weston Thatcher Borden, The effects of orbital interactions on the geometries of some annelated benzenes, Theoretical Chemistry Accounts, 2011, 130, 2-3, 261CrossRef
  16. 16Weston Thatcher Borden, With a Little Help from My Friends: Forty Years of Fruitful Chemical Collaborations, The Journal of Organic Chemistry, 2011, 76, 9, 2943CrossRef
  17. 17Junfa Wei, Bo Han, Qiang Guo, Xianying Shi, Wenliang Wang, Ni Wei, 1,5,9-Triazacoronenes: A Family of Polycyclic Heteroarenes Synthesized by a Threefold Pictet-Spengler Reaction, Angewandte Chemie, 2010, 122, 44, 8385Wiley Online Library
  18. 18Junfa Wei, Bo Han, Qiang Guo, Xianying Shi, Wenliang Wang, Ni Wei, 1,5,9-Triazacoronenes: A Family of Polycyclic Heteroarenes Synthesized by a Threefold Pictet-Spengler Reaction, Angewandte Chemie International Edition, 2010, 49, 44, 8209Wiley Online Library
  19. 19Georg Jansen, Björn Kahlert, Frank-Gerrit Klärner, Roland Boese, Dieter Bläser, Intramolecular Electronic Interactions between Nonconjugated Arene and Quinone Chromophores, Journal of the American Chemical Society, 2010, 132, 25, 8581CrossRef
  20. 20Tsun-Cheng Wu, Chia-Hua Chen, Daijiro Hibi, Akihiro Shimizu, Yoshito Tobe, Yao-Ting Wu, Synthesis, Structure, and Photophysical Properties of Dibenzo[de,mn]naphthacenes, Angewandte Chemie International Edition, 2010, 49, 39, 7059Wiley Online Library

View all 64 citations