Full Paper

Configurationally Stable Tris(tetrathioaryl)methyl Molecular Propellers

  1. Benoît Driesschaert1,2,
  2. Raphaël Robiette1,
  3. Cécile S. Le Duff1,
  4. Laurent Collard1,
  5. Koen Robeyns1,
  6. Bernard Gallez2,
  7. Jacqueline Marchand-Brynaert1

Article first published online: 9 AUG 2012

DOI: 10.1002/ejoc.201200801

Issue

European Journal of Organic Chemistry

European Journal of Organic Chemistry

Volume 2012, Issue 33, pages 6517–6525, November 2012

Additional Information

How to Cite

Driesschaert, B., Robiette, R., Le Duff, C. S., Collard, L., Robeyns, K., Gallez, B. and Marchand-Brynaert, J. (2012), Configurationally Stable Tris(tetrathioaryl)methyl Molecular Propellers. Eur. J. Org. Chem., 2012: 6517–6525. doi: 10.1002/ejoc.201200801

Author Information

  1. 1

    Institute of Condensed Matter and Nanosciences (IMCN), Molecules, Solids and Reactivity (MOST), Université catholique de Louvain, Place Louis Pasteur 1, L4.01.02, 1348 Louvain-la-Neuve, Belgium, Fax: +32-10-474168, http://www.uclouvain.be/en-267015.html

  2. 2

    Louvain Drug Research Institute (LDRI), Biomedical Magnetic Resonance Section (REMA), Université catholique de Louvain, avenue Mounier 73, B1.73.08, 1200 Bruxelles, Belgium

Publication History

  1. Issue published online: 12 NOV 2012
  2. Article first published online: 9 AUG 2012
  3. Manuscript Received: 15 JUN 2012

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Keywords:

  • Isomerization;
  • Molecular propeller;
  • EXSY;
  • CSP-HPLC;
  • Density functional calculations;
  • Conformation analysis

Abstract

Tris(tetrathioaryl)methanols and tris(tetrathioaryl)methanes are direct precursors and metabolites, respectively, of tris(tetrathioaryl)methyl radicals, which are very attractive paramagnetic spin probes for many magnetic resonance applications. Due to steric hindrance, these propeller-shaped molecules display slow interconversion between their two enantiomeric conformations (right-handed and left-handed propeller conformations). Syntheses and HPLC resolutions carried out on a chiral stationary phase have been achieved. The influence of the hybridization of the central carbon atom as well as the para substitutient on the conformational stability were experimentally and theoretically studied. Depending on their particular structure, the free activation energy for the isomerization process determined by kinetics of racemization varies from 24.4 to 26.4 kcal mol–1 and corresponds to racemization half-lives of 12 and 343 h, respectively. Computational and NOESY/exchange spectroscopy (EXSY) studies are consistent with a two-ring flip mechanism for the isomerization process of tris(tetrathioaryl)methanols, radicals and tris(tetrathioaryl)methanes.

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