skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Stabilizing a different cyclooctatetraene stereoisomer

Abstract

An unconventional cis-cis-cis-trans or (Z,Z,Z,E) structure B of cyclooctatetraene (COT) is calculated to lie only 23 kcal/mol above the well-known tub-shaped (Z,Z,Z,Z) isomer A; one example of this type of structure is known. The barrier for B returning to A is small, 3 kcal/mol. However, by suitable choice of substituents, the (Z,Z,Z,E) isomer can be made to lie in energy below the tub-shaped structure. Steric, clamping, and electronic strategies are proposed for achieving this. In the steric strategy, the C 8 H 4 (CH 3 ) 2 (C( t Bu) 3 ) 2 structure B is predicted to lie 21 kcal/mol below structure A, which is separated from form B only by a small barrier. A simple clamping strategy, effective for COT planarization, does not influence the A/B isomerization much. But, if the clamping group is aromatic (a fused benzene, pyrrole, thiophene, furan), the subtle interplay of potential aromaticity with clamping can be used to confer persistence if not stability on the (Z,Z,Z,E) isomer. An electronic strategy of a different kind, push–pull substitution on the COT ring, was not very effective in stabilizing the B form. However, it led us to vicinal amine–borane-substituted normal COTs that proved tomore » be quite good at activating H 2 in a frustrated Lewis pair scenario.« less

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Univ. of Georgia, Athens, GA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1377094
Alternate Identifier(s):
OSTI ID: 1466011
Grant/Contract Number:  
SC0015512
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 114 Journal Issue: 37; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; cyclooctatetraene; steric effects; electronic effects; frustrated Lewis pair; molecular orbital theory

Citation Formats

Li, Longfei, Lei, Ming, Xie, Yaoming, Schaefer, III, Henry F., Chen, Bo, and Hoffmann, Roald. Stabilizing a different cyclooctatetraene stereoisomer. United States: N. p., 2017. Web. https://doi.org/10.1073/pnas.1709586114.
Li, Longfei, Lei, Ming, Xie, Yaoming, Schaefer, III, Henry F., Chen, Bo, & Hoffmann, Roald. Stabilizing a different cyclooctatetraene stereoisomer. United States. https://doi.org/10.1073/pnas.1709586114
Li, Longfei, Lei, Ming, Xie, Yaoming, Schaefer, III, Henry F., Chen, Bo, and Hoffmann, Roald. Mon . "Stabilizing a different cyclooctatetraene stereoisomer". United States. https://doi.org/10.1073/pnas.1709586114.
@article{osti_1377094,
title = {Stabilizing a different cyclooctatetraene stereoisomer},
author = {Li, Longfei and Lei, Ming and Xie, Yaoming and Schaefer, III, Henry F. and Chen, Bo and Hoffmann, Roald},
abstractNote = {An unconventional cis-cis-cis-trans or (Z,Z,Z,E) structure B of cyclooctatetraene (COT) is calculated to lie only 23 kcal/mol above the well-known tub-shaped (Z,Z,Z,Z) isomer A; one example of this type of structure is known. The barrier for B returning to A is small, 3 kcal/mol. However, by suitable choice of substituents, the (Z,Z,Z,E) isomer can be made to lie in energy below the tub-shaped structure. Steric, clamping, and electronic strategies are proposed for achieving this. In the steric strategy, the C 8 H 4 (CH 3 ) 2 (C( t Bu) 3 ) 2 structure B is predicted to lie 21 kcal/mol below structure A, which is separated from form B only by a small barrier. A simple clamping strategy, effective for COT planarization, does not influence the A/B isomerization much. But, if the clamping group is aromatic (a fused benzene, pyrrole, thiophene, furan), the subtle interplay of potential aromaticity with clamping can be used to confer persistence if not stability on the (Z,Z,Z,E) isomer. An electronic strategy of a different kind, push–pull substitution on the COT ring, was not very effective in stabilizing the B form. However, it led us to vicinal amine–borane-substituted normal COTs that proved to be quite good at activating H 2 in a frustrated Lewis pair scenario.},
doi = {10.1073/pnas.1709586114},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 37,
volume = 114,
place = {United States},
year = {2017},
month = {8}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1073/pnas.1709586114

Citation Metrics:
Cited by: 3 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Efficient Synthesis of Benzene and Planar Cyclooctatetraene Fully Annelated with Bicyclo[2.1.1]hex-2-ene
journal, February 2001

  • Matsuura, Akira; Komatsu, Koichi
  • Journal of the American Chemical Society, Vol. 123, Issue 8
  • DOI: 10.1021/ja003512m

Thermal and photochemical interconversions of cyclooctatetraenes and semibullvalenes. Exploratory organic photochemistry. LII
journal, April 1970

  • Zimmerman, Howard E.; Iwamura, Hiizu.
  • Journal of the American Chemical Society, Vol. 92, Issue 7
  • DOI: 10.1021/ja00710a038

9,9',10,10'-Tetradehydrodianthracene. Formation, protection, and regeneration of a strained double bond
journal, June 1974

  • Viavattene, Ronald L.; Greene, Frederick D.; Cheung, L. D.
  • Journal of the American Chemical Society, Vol. 96, Issue 13
  • DOI: 10.1021/ja00820a058

Synthesis of Cyclooctatetraenes through a Palladium-Catalyzed Cascade Reaction
journal, May 2016

  • Blouin, Sarah; Gandon, Vincent; Blond, Gaëlle
  • Angewandte Chemie International Edition, Vol. 55, Issue 25
  • DOI: 10.1002/anie.201602586

Perfluorotetracyclobutacyclo-octatetraene; a planar eight-membered ring system; X-ray crystal structure
journal, January 1981

  • Einstein, Frederick W. B.; Willis, Anthony C.; Cullen, William R.
  • Journal of the Chemical Society, Chemical Communications, Issue 11
  • DOI: 10.1039/c39810000526

PM3 and ab initio studies of the C8H8 potential energy surface. Thermal isomerism of syn- and anti-tricyclo[4.2.0.02,5]octa-3,7-dienes †
journal, January 1998

  • Conesa, Carlota; Rzepa, Henry S.
  • Journal of the Chemical Society, Perkin Transactions 2, Issue 4
  • DOI: 10.1039/a708165k

Approaches to “Push-Pull” Stabilized Cyclobutadienes 1
journal, November 1965

  • Breslow, Ronald; Kivelevich, Doris; Mitchell, Michael J.
  • Journal of the American Chemical Society, Vol. 87, Issue 22
  • DOI: 10.1021/ja00950a027

On the Mechanism of Hydrogen Activation by Frustrated Lewis Pairs
journal, November 2013

  • Zeonjuk, Lei Liu; Vankova, Nina; Mavrandonakis, Andreas
  • Chemistry - A European Journal, Vol. 19, Issue 51
  • DOI: 10.1002/chem.201302727

Structure of Cyclo-octatetraene
journal, January 1948

  • Kaufman, H. S.; Fankuchen, I.; Mark, H.
  • Nature, Vol. 161, Issue 4083
  • DOI: 10.1038/161165a0

Planarization of 1,3,5,7-cyclooctatetraene as a result of a partial rehybridization at carbon atoms: an MP2/6-31G∗ and B3LYP/6-311G∗∗ study
journal, June 2002

  • Krygowski, Tadeusz M.; Pindelska, Edyta; Cyrański, Michał K.
  • Chemical Physics Letters, Vol. 359, Issue 1-2
  • DOI: 10.1016/S0009-2614(02)00681-4

Recent Studies on the Aromaticity and Antiaromaticity of Planar Cyclooctatetraene
journal, February 2010

  • Nishinaga, Tohru; Ohmae, Takeshi; Iyoda, Masahiko
  • Symmetry, Vol. 2, Issue 1
  • DOI: 10.3390/sym2010076

Möbius aromaticity in small [ n ] trans -annulenes? : Möbius Aromaticity in Small [
journal, January 2001

  • Havenith, Remco W. A.; van Lenthe, Joop H.; Jenneskens, Leonardus W.
  • International Journal of Quantum Chemistry, Vol. 85, Issue 1
  • DOI: 10.1002/qua.1089

Molecular and Valence Structures of Complexes of Cyclo‐Octatetraene with Iron Tricarbonyl
journal, November 1962

  • Dickens, Brian; Lipscomb, William N.
  • The Journal of Chemical Physics, Vol. 37, Issue 9
  • DOI: 10.1063/1.1733429

CASSCF calculations find that a D8h geometry is the transition state for double bond shifting in cyclooctatetraene
journal, July 1992

  • Hrovat, David A.; Borden, Weston Thatcher
  • Journal of the American Chemical Society, Vol. 114, Issue 14
  • DOI: 10.1021/ja00040a071

Reaction of a P/Al-Based Frustrated Lewis Pair with Ammonia, Borane, and Amine-Boranes: Adduct Formation and Catalytic Dehydrogenation
journal, March 2013

  • Appelt, Christian; Slootweg, J. Chris; Lammertsma, Koop
  • Angewandte Chemie International Edition, Vol. 52, Issue 15
  • DOI: 10.1002/anie.201208746

Facile Heterolytic H 2 Activation by Amines and B(C 6 F 5 ) 3
journal, July 2008

  • Sumerin, Victor; Schulz, Felix; Nieger, Martin
  • Angewandte Chemie International Edition, Vol. 47, Issue 32
  • DOI: 10.1002/anie.200800935

Catalytic B–N Dehydrogenation Using Frustrated Lewis Pairs: Evidence for a Chain-Growth Coupling Mechanism
journal, March 2016

  • Mo, Zhenbo; Rit, Arnab; Campos, Jesús
  • Journal of the American Chemical Society, Vol. 138, Issue 10
  • DOI: 10.1021/jacs.6b01170

Paratropic Delocalized Ring Currents in Flattened Cyclooctatetraene Systems with Bond Alternation
journal, May 2002


Ground states of conjugated molecules–XXI
journal, January 1970


Benzene fused five-membered heterocycles. A theoretical approach
journal, August 2003


Preparation of 1,4,5,8-tetra-tert-butyl-1,3,5,7-cyclooctatetraene by twofold SO2 extrusion
journal, October 2003


Enhanced Basicity of Push–Pull Nitrogen Bases in the Gas Phase
journal, October 2016


Hyperconjugation in hydrocarbons: Not just a “mild sort of conjugation”
journal, April 2013


Deeper Insight into the Factors Controlling H 2 Activation by Geminal Aminoborane-Based Frustrated Lewis Pairs
journal, November 2016

  • Yepes, Diana; Jaque, Pablo; Fernández, Israel
  • Chemistry - A European Journal, Vol. 22, Issue 52
  • DOI: 10.1002/chem.201603889

The Important Role of Heteroaromatics in the Design of Efficient Second-Order Nonlinear Optical Molecules:  Theoretical Investigation on Push−Pull Heteroaromatic Stilbenes
journal, January 1996

  • Varanasi, Pushkara Rao; Jen, Alex K. -Y.; Chandrasekhar, J.
  • Journal of the American Chemical Society, Vol. 118, Issue 49
  • DOI: 10.1021/ja960136q

A theoretical investigation of the Frustrated Lewis Pairs of C/P and B/N in the metal-free hydrogen-storage compounds
journal, November 2016


Accurate Determination of the Structure of Cyclooctatetraene by Femtosecond Rotational Coherence Spectroscopy and ab Initio Calculations
journal, September 2008

  • Kummli, Dominique S.; Lobsiger, Simon; Frey, Hans-Martin
  • The Journal of Physical Chemistry A, Vol. 112, Issue 38
  • DOI: 10.1021/jp803523y

Cyclooctatetraene Computational Photo- and Thermal Chemistry:  A Reactivity Model for Conjugated Hydrocarbons
journal, November 2002

  • Garavelli, Marco; Bernardi, Fernando; Cembran, Alessandro
  • Journal of the American Chemical Society, Vol. 124, Issue 46
  • DOI: 10.1021/ja020741v

Transition-State Spectroscopy of Cyclooctatetraene
journal, June 1996


Multireference calculations for ring inversion and double bond shifting in cyclooctatetraene
journal, March 2013

  • Schild, Axel; Paulus, Beate
  • Journal of Computational Chemistry, Vol. 34, Issue 16
  • DOI: 10.1002/jcc.23273

Helical (5Z, 11E)-Dibenzo[a,e]cyclooctatetrene: A Spring-Loaded Monomer
journal, April 2008

  • Carnes, Matthew; Buccella, Daniela; Decatur, John
  • Angewandte Chemie International Edition, Vol. 47, Issue 16
  • DOI: 10.1002/anie.200704355

Molecular Tweezers for Hydrogen: Synthesis, Characterization, and Reactivity
journal, October 2008

  • Sumerin, Victor; Schulz, Felix; Atsumi, Michiko
  • Journal of the American Chemical Society, Vol. 130, Issue 43
  • DOI: 10.1021/ja806627s

On the Mechanism of B(C 6 F 5 ) 3 -Catalyzed Direct Hydrogenation of Imines: Inherent and Thermally Induced Frustration
journal, February 2009

  • Rokob, Tibor András; Hamza, Andrea; Stirling, András
  • Journal of the American Chemical Society, Vol. 131, Issue 5
  • DOI: 10.1021/ja809125r

Über Cyclo-octatetraen
journal, July 1911

  • Willstätter, Richard; Waser, Ernst
  • Berichte der deutschen chemischen Gesellschaft, Vol. 44, Issue 3
  • DOI: 10.1002/cber.191104403216

Probable trans-cyclooctatetraene
journal, January 1969

  • White, Emil H.; Friend, Earl W.; Stern, Robert L.
  • Journal of the American Chemical Society, Vol. 91, Issue 2
  • DOI: 10.1021/ja01030a068

Frustrated Lewis Pairs: Metal-free Hydrogen Activation and More
journal, December 2009

  • Stephan, Douglas W.; Erker, Gerhard
  • Angewandte Chemie International Edition, Vol. 49, Issue 1
  • DOI: 10.1002/anie.200903708

Experimental and theoretical treatment of hydrogen splitting and storage in boron–nitrogen systems
journal, August 2009


Demonstration of fourfold rotational barriers in push-pull ethylenes
journal, June 1977

  • Sandstrom, Jan; Sjostrand, Ulf; Wennerbeck, Ingegerd
  • Journal of the American Chemical Society, Vol. 99, Issue 13
  • DOI: 10.1021/ja00455a064

Diazadioxa[8]circulenes: Planar Antiaromatic Cyclooctatetraenes
journal, November 2013

  • Hensel, Thomas; Trpcevski, Denis; Lind, Christopher
  • Chemistry - A European Journal, Vol. 19, Issue 50
  • DOI: 10.1002/chem.201303194

Isotope Effects on the Ring Inversion of Cyclooctatetraene
journal, September 1998

  • Stevenson, Cheryl D.; Brown, Eric C.; Hrovat, David A.
  • Journal of the American Chemical Society, Vol. 120, Issue 34
  • DOI: 10.1021/ja981496b

Potential energy surface of cyclooctatetraene
journal, January 1998

  • Andrés, José L.; Castaño, Obis; Morreale, Antonio
  • The Journal of Chemical Physics, Vol. 108, Issue 1
  • DOI: 10.1063/1.475388

Does chair cyclo-octatetraene exist?
journal, January 1985

  • Dewar, Michael J. S.; Merz, Kenneth M.
  • Journal of the Chemical Society, Chemical Communications, Issue 6
  • DOI: 10.1039/c39850000343

Turning Frustration into Bond Activation: A Theoretical Mechanistic Study on Heterolytic Hydrogen Splitting by Frustrated Lewis Pairs
journal, March 2008

  • Rokob, Tibor András; Hamza, Andrea; Stirling, András
  • Angewandte Chemie International Edition, Vol. 47, Issue 13
  • DOI: 10.1002/anie.200705586

Paratropic Delocalized Ring Currents in Flattened Cyclooctatetraene Systems with Bond Alternation
journal, May 2002


Helical (5Z, 11E)-Dibenzo[a,e]cyclooctatetrene: A Spring-Loaded Monomer
journal, April 2008

  • Carnes, Matthew; Buccella, Daniela; Decatur, John
  • Angewandte Chemie, Vol. 120, Issue 16
  • DOI: 10.1002/ange.200704355

Turning Frustration into Bond Activation: A Theoretical Mechanistic Study on Heterolytic Hydrogen Splitting by Frustrated Lewis Pairs
journal, March 2008

  • Rokob, Tibor András; Hamza, Andrea; Stirling, András
  • Angewandte Chemie, Vol. 120, Issue 13
  • DOI: 10.1002/ange.200705586

    Works referencing / citing this record:

    Refereeing data for article PNAS MS# 2017-09586P entitled "A New Structure for Cyclooctatetraene"
    dataset, June 2017

    • Rzepa, Henry
    • Imperial College London-Supplementary information for journal article at DOI: 10.1073/pnas.1709586114, 5 files
    • DOI: 10.14469/HPC/2640

    Rational Design of a Carbon‐Boron Frustrated Lewis Pair for Metal‐free Dinitrogen Activation
    journal, March 2019


    Mechanisms of Ketone/Imine Hydrogenation Catalyzed by Transition‐Metal Complexes
    journal, September 2019

    • Liu, Yangqiu; Yue, Xin; Luo, Chenguang
    • ENERGY & ENVIRONMENTAL MATERIALS, Vol. 2, Issue 4
    • DOI: 10.1002/eem2.12050

    Conformational preferences and isomerization upon excitation/ionization of 2-methoxypyridine and 2- N -methylaminopyridine
    journal, January 2018

    • Dai, Wenshuai; Liu, Sheng; Zhang, Zhe
    • Physical Chemistry Chemical Physics, Vol. 20, Issue 9
    • DOI: 10.1039/c7cp07854d

    Theoretical calculations of the chemical shifts of cyclo[n]phosphazenes for n = 2, 3, 4 and 5 (X 2 PN) n with X = CH 3 , F, Cl and Br: the effect of relativistic corrections
    journal, November 2019