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Anomalous nuclear overhauser effects in carbon-substituted aziridines: scalar cross-relaxation of the first kind

Anomalous nuclear overhauser effects in carbon-substituted aziridines: scalar cross-relaxation of the first kind
Anomalous nuclear overhauser effects in carbon-substituted aziridines: scalar cross-relaxation of the first kind
Anomalous NOESY cross-peaks that cannot be explained by dipolar cross-relaxation or chemical exchange are described for carbon-substituted aziridines. The origin of these is identified as scalar cross-relaxation of the first kind, as demonstrated by a complete theoretical description of this relaxation process and by computational simulation of the NOESY spectra. It is shown that this process relies on the stochastic modulation of J-coupling by conformational transitions, which in the case of aziridines arise from inversion at the nitrogen center. The observation of scalar cross-relaxation between protons does not appear to have been previously reported for NOESY spectra. Conventional analysis would have assigned the cross-peaks as being indicative of a chemical exchange process occurring between correlated spins, were it not for the fact that the pairs of nuclei displaying them cannot undergo such exchange.
1433-7851
3697-3701
Kuprov, Ilya
bb07f28a-5038-4524-8146-e3fc8344c065
Hodgson, David M.
04c7a861-68b5-4d8c-a983-f067b2d58857
Kloesges, Johannes
1bf90ecb-6c99-4124-9ee6-c738217685d6
Pearson, Christopher I.
bfc7281f-bfdf-480a-b25c-42c5a8126a8b
Odell, Barbara
b98ac430-5f30-4ff4-9b7f-9ae66ac9a2c2
Claridge, Timothy D.W.
c7583cca-a2f9-4ae2-8f78-66512a279f15
Kuprov, Ilya
bb07f28a-5038-4524-8146-e3fc8344c065
Hodgson, David M.
04c7a861-68b5-4d8c-a983-f067b2d58857
Kloesges, Johannes
1bf90ecb-6c99-4124-9ee6-c738217685d6
Pearson, Christopher I.
bfc7281f-bfdf-480a-b25c-42c5a8126a8b
Odell, Barbara
b98ac430-5f30-4ff4-9b7f-9ae66ac9a2c2
Claridge, Timothy D.W.
c7583cca-a2f9-4ae2-8f78-66512a279f15

Kuprov, Ilya, Hodgson, David M., Kloesges, Johannes, Pearson, Christopher I., Odell, Barbara and Claridge, Timothy D.W. (2015) Anomalous nuclear overhauser effects in carbon-substituted aziridines: scalar cross-relaxation of the first kind. Angewandte Chemie International Edition, 54 (12), 3697-3701. (doi:10.1002/anie.201410271).

Record type: Article

Abstract

Anomalous NOESY cross-peaks that cannot be explained by dipolar cross-relaxation or chemical exchange are described for carbon-substituted aziridines. The origin of these is identified as scalar cross-relaxation of the first kind, as demonstrated by a complete theoretical description of this relaxation process and by computational simulation of the NOESY spectra. It is shown that this process relies on the stochastic modulation of J-coupling by conformational transitions, which in the case of aziridines arise from inversion at the nitrogen center. The observation of scalar cross-relaxation between protons does not appear to have been previously reported for NOESY spectra. Conventional analysis would have assigned the cross-peaks as being indicative of a chemical exchange process occurring between correlated spins, were it not for the fact that the pairs of nuclei displaying them cannot undergo such exchange.

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e-pub ahead of print date: 28 January 2015
Published date: 10 March 2015
Organisations: Computational Systems Chemistry, Magnetic Resonance

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Local EPrints ID: 395545
URI: https://eprints.soton.ac.uk/id/eprint/395545
ISSN: 1433-7851
PURE UUID: 891819d2-d36a-4557-867a-e4d19ead289a
ORCID for Ilya Kuprov: ORCID iD orcid.org/0000-0003-0430-2682

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Date deposited: 31 May 2016 15:54
Last modified: 14 Jul 2018 00:30

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