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D-HMBC versus LR-HSQMBC: Which experiment provides theoretically and experimentally the best results?

  • Bigler P Departement für Chemie und Biochemie, Universität Bern, Bern, Switzerland.
  • Furrer J Departement für Chemie und Biochemie, Universität Bern, Bern, Switzerland.
  • 2018-12-01
Published in:
  • Magnetic resonance in chemistry : MRC. - 2018
13C
1H
D-HMBC
LR-HSQMBC
NMR
cross peak intensity
homonuclear couplings
product operator
English The long-range heteronuclear single quantum multiple bond correlation (LR-HSQMBC) experiment is the experiment of choice for visualizing heteronuclear long-range coupling interactions n JCH across 4-6-bonds and is experimentally superior to the decoupled heteronuclear multiple-bond correlation (D-HMBC) experiment. Yet, the exact reasons have not been fully understood and established. On the basis of our recent investigation of the nonrefocused variants LR-HSQC and HMBC, we have extended a JHH' -dedicated investigation to the D-HMBC and LR-HSQMBC experiments. Unlike the nonrefocused variants, the influence of homonuclear couplings JHH' on the intensity of long-range n JCH cross-peaks is not easily predictable and may be summarized as follows: (a) irrespective of the magnitude and number of JHH' interactions long-range n JCH cross-peaks are more intense in D-HMBC spectra as long as the evolution delay Δ is not too large, because in contrast to LR-HSQMBC no JHH' -caused intensity zeroes will occur. (b) If JHH' is small and Δ large, the intensity of cross peaks in D-HMBC spectra may be weakened or may even vanish at Δ = (0.25+0.5k)/JHH ', whereas for the LR-HSQMBC this unwanted effect occurs at Δ = k + 0.5/JHH' . Consequently, when Δ is adjusted to visualize weak n JCH long-range correlations, our findings corroborate that there are potentially more cross-peaks expected to show up in a LR-HSQMBC spectrum compared with a D-HMBC spectrum. This has been indeed noticed experimentally, even though the intensity of a many long-range n JCH cross-peaks may still be higher in the spectra of the D-HMBC experiment correspondingly adjusted for detecting weak n JCH correlations.
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https://sonar.ch/global/documents/264042
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