logo

OR SEARCH CITATIONS

My Activity
Publications
CONTENT TYPES

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:J. Phys. Chem. A 2003, 107, 8, 1175-1180
RETURN TO ISSUEPREVArticleNEXT

Cope Rearrangement of 1,5-Hexadiene:  Full Geometry Optimizations Using Analytic MR-CISD and MR-AQCC Gradient Methods

View Author Information
Institute for Theoretical Chemistry and Structural Biology, University of Vienna, Währingerstrasse 17, A-1090, Austria
Cite this: J. Phys. Chem. A 2003, 107, 8, 1175–1180
Publication Date (Web):January 30, 2003
https://doi.org/10.1021/jp0259014
Copyright © 2003 American Chemical Society
RIGHTS & PERMISSIONS
Article Views
301
Altmetric
-
Citations
22
LEARN ABOUT THESE METRICS
Read OnlinePDF (86 KB)
Get e-Alerts
Supporting Info (1)»
SUBJECTS:

Abstract

Full geometry optimizations within given molecular symmetries have been performed on the chair and boat forms involved in the Cope rearrangement of 1,5-hexadiene using highly correlated methods (MR-CISD and MR-AQCC) and extended basis sets. These optimizations are based on analytic gradient procedures developed within the COLUMBUS program system and are the first ones for the Cope rearrangement, which have been carried out at a multireference, post-CASSCF level. By comparison of MR-CISD and MR-AQCC results, the importance of size-extensivity corrections is clearly demonstrated. Computed energetic stabilities with respect to 1,5-hexadiene and bis-allyl are in good agreement with experimental data. Only a single saddle point for the chair form of C2h symmetry is found in contrast to CASSCF results, but in agreement with CASPT2N and MRMP2 investigations. Thus, we confirm these previous results showing that the mechanism of the Cope rearrangement of 1,5-hexadiene is concerted via an aromatic transition state.

*

 To whom correspondence should be addressed.

†

 E-mail:  [email protected]

‡

 E-mail:  [email protected]

Supporting Information Available

ARTICLE SECTIONS
Jump To

MR-AQCC energies and Cartesian geometries for chair and boat structures and for 1,5-hexadiene optimized at the MR-AQCC level using different basis sets. This material is available free of charge via the Internet at http://pubs.acs.org.

Terms & Conditions

Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

Cited By

This article is cited by 22 publications.

  1. Dinesh V. Vidhani, Igor V. Alabugin. Controlled Evolution of the Cope Rearrangement: Transition from Concerted to Interrupted and Aborted Pericyclic Reactions Regulated by a Switch Built from an Intramolecular Frustrated Lewis Pair. The Journal of Organic Chemistry 2019, 84 (22) , 14844-14853. https://doi.org/10.1021/acs.joc.9b02633
  2. Jorge Escorihuela, Anita Das, Wilhelmus J. E. Looijen, Floris L. van Delft, Adelia J. A. Aquino, Hans Lischka, and Han Zuilhof . Kinetics of the Strain-Promoted Oxidation-Controlled Cycloalkyne-1,2-quinone Cycloaddition: Experimental and Theoretical Studies. The Journal of Organic Chemistry 2018, 83 (1) , 244-252. https://doi.org/10.1021/acs.joc.7b02614
  3. Timm Bredtmann and Beate Paulus . Electron–Nuclear Motion in the Cope Rearrangement of Semibullvalene: Ever Synchronous?. Journal of Chemical Theory and Computation 2013, 9 (7) , 3026-3034. https://doi.org/10.1021/ct400318z
  4. Péter G. Szalay , Thomas Müller , Gergely Gidofalvi , Hans Lischka , Ron Shepard . Multiconfiguration Self-Consistent Field and Multireference Configuration Interaction Methods and Applications. Chemical Reviews 2012, 112 (1) , 108-181. https://doi.org/10.1021/cr200137a
  5. Şeref Gül, Franziska Schoenebeck, Viktorya Aviyente and K. N. Houk . Computational Study of Factors Controlling the Boat and Chair Transition States of Ireland−Claisen Rearrangements. The Journal of Organic Chemistry 2010, 75 (6) , 2115-2118. https://doi.org/10.1021/jo100033d
  6. Jingsong Huang and, Miklos Kertesz. Stepwise Cope Rearrangement of Cyclo-biphenalenyl via an Unusual Multicenter Covalent π-Bonded Intermediate. Journal of the American Chemical Society 2006, 128 (22) , 7277-7286. https://doi.org/10.1021/ja060427r
  7. Joshua J. Blavins,, David L. Cooper, and, Peter B. Karadakov. Aromatic vs Diradical Character in the Transition States of the Cope Rearrangements of 1,5-Hexadiene and Its Cyano Derivatives. The Journal of Physical Chemistry A 2004, 108 (1) , 194-202. https://doi.org/10.1021/jp036660i
  8. Sinead T. Keaveney, Ronald S. Haines, Jason B. Harper. Investigating Solvent Effects of an Ionic Liquid on Pericyclic Reactions through Kinetic Analyses of Simple Rearrangements. ChemPlusChem 2017, 82 (3) , 449-457. https://doi.org/10.1002/cplu.201600585
  9. Huajun Chen, Xin Lu Cheng, Hao Liu, Jie Wu. Studies on the electric dipole moment function and line parameters for high overtone bands of NO. Journal of Quantitative Spectroscopy and Radiative Transfer 2014, 142 , 49-57. https://doi.org/10.1016/j.jqsrt.2014.03.015
  10. . Pericyclic Reactions. 2014,,, 197-295. https://doi.org/10.1002/9781118671191.ch4
  11. Huajun Chen, Xinlu Cheng, Hao Liu, Jie Wu, Cuiming Tang. WITHDRAWN: The accurate transition dipole moment and line intensities of NO(X2Π) based on averaged quadratic coupled-cluster calculations. Journal of Molecular Spectroscopy 2013, https://doi.org/10.1016/j.jms.2013.10.003
  12. . Cope Rearrangement. 2010,,https://doi.org/10.1002/9780470638859.conrr154
  13. Yuanzhi Xia, Fengying Zhou, Yahong Li, Wu Li. Effect of electron-withdrawing group on the [3,3]-sigmatropic rearrangements of 1,5-enynes, 1,5-diynes and 1,2-diene-5-ynes: A theoretical study. Journal of Molecular Structure: THEOCHEM 2009, 904 (1-3) , 69-73. https://doi.org/10.1016/j.theochem.2009.02.033
  14. William N. Setzer. Ab initio analysis of the Cope rearrangement of germacrane sesquiterpenoids. Journal of Molecular Modeling 2008, 14 (5) , 335-342. https://doi.org/10.1007/s00894-008-0274-3
  15. Juracy R. Lucena, Elizete Ventura, Silmar A. do Monte, Regiane C. M. U. Araújo, Mozart N. Ramos, Rui Fausto. Dissociation of ground and nσ* states of CF3Cl using multireference configuration interaction with singles and doubles and with multireference average quadratic coupled cluster extensivity corrections. The Journal of Chemical Physics 2007, 127 (16) , 164320. https://doi.org/10.1063/1.2800020
  16. Victor Polo, Juan Andrés. A joint study based on the electron localization function and catastrophe theory of the chameleonic and centauric models for the Cope rearrangement of 1,5-hexadiene and its cyano derivatives. Journal of Computational Chemistry 2005, 26 (14) , 1427-1437. https://doi.org/10.1002/jcc.20272
  17. Xinzheng Yang, Meirong Lin, Baozheng Zhang. An ab initio study of the ground and valence excited states of GaF. The Journal of Chemical Physics 2004, 120 (9) , 4289-4296. https://doi.org/10.1063/1.1643718
  18. Kathleen M. Morgan. 12  Reaction mechanisms : Part (iii) Pericyclic reactions. Annu. Rep. Prog. Chem., Sect. B: Org. Chem. 2004, 100 , 335-350. https://doi.org/10.1039/B402173H
  19. Brian F. Yates. 11  Computational organic chemistry. Annu. Rep. Prog. Chem., Sect. B: Org. Chem. 2004, 100 , 251-283. https://doi.org/10.1039/B404044A
  20. Xinzheng Yang, Meirong Lin, Wenli Zou, Baozheng Zhang. An ab initio study of the ground and valence excited states of GaCl. Journal of Physics B: Atomic, Molecular and Optical Physics 2003, 36 (23) , 4651-4665. https://doi.org/10.1088/0953-4075/36/23/005
  21. Xinzheng Yang, Meirong Lin, Baozheng Zhang. MR-AQCC study on the ground and low-lying excited states of GaI. Chemical Physics Letters 2003, 382 (1-2) , 160-166. https://doi.org/10.1016/j.cplett.2003.10.059
  22. Elizete Ventura, Michal Dallos, Hans Lischka. Revisiting the stationary points on the potential energy surface of tetramethylene at the MR-AQCC level using analytic gradients. The Journal of Chemical Physics 2003, 118 (24) , 10963-10972. https://doi.org/10.1063/1.1575191

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

You’ve supercharged your research process with ACS and Mendeley!

STEP 1:
Click to create an ACS ID

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

MENDELEY PAIRING EXPIRED
Your Mendeley pairing has expired. Please reconnect

This website uses cookies to improve your user experience. By continuing to use the site, you are accepting our use of cookies. Read the ACS privacy policy.

CONTINUE