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Deuterium NMR 2D Exchange Spectroscopy in Liquid Crystalline Solutions and Its Application to the Cope Rearrangement in Bullvalene

MPG-Autoren
http://pubman.mpdl.mpg.de/cone/persons/resource/persons128263

Zimmermann,  Herbert
Department of Molecular Physics, Max Planck Institute for Medical Research, Max Planck Society;
Department of Biomolecular Mechanisms, Max Planck Institute for Medical Research, Max Planck Society;
Zimmermann Group, Max Planck Institute for Medical Research, Max Planck Society;
Emeritus Group Biophysics, Max Planck Institute for Medical Research, Max Planck Society;

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Zitation

Boeffel, C., Luz, Z., Poupko, R., & Zimmermann, H. (1989). Deuterium NMR 2D Exchange Spectroscopy in Liquid Crystalline Solutions and Its Application to the Cope Rearrangement in Bullvalene. Journal of Magnetic Resonance, 85, 329-336. doi:10.1016/0022-2364(89)90147-9.


Zusammenfassung
The method of 2D exchange NMR spectroscopy is applied to deuterium spectra of bullvalene−d10 dissolved in a nematic solvent. The 2D spectra were obtained by combining Zeeman− and quadrupole−order experiments, using three−pulse sequences consisting of a View the MathML source excitation pulse followed by 54.7° alignment and monitoring pulses. The measurements were done at 5°C where the Cope−rearrangement reaction in bullvalene is too slow to affect the width of the lines, yet sufficiently fast to yield exchange cross peaks. The intensities of the diagonal and cross peaks were measured as function of the mixing time in the three−pulse sequences. A theoretical analysis of the expected dependence of the peak intensities on the mixing time in the presence of the Cope rearrangement is presented and the results are compared with those of the experiments