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Analysis of 2D Maps Based on Similarity in DFT-Calculated vs Experimental 13C–15N Spin Couplings for a Representative Sample of Conformationally Rigid and Structurally Fixed Nitrogen-Containing Organic Compounds

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Abstract

In this work, we carried out an extended verification of the 13C–15N spin–spin coupling constants as a new structural indicator of nitrogen-containing organic compounds. In this regard, we performed a quantum-chemical calculation (B3LYP with basis set 6-311++G(2df,2p)) for a representative sample of 193 spin–spin couplings for the currently known literature experimental data on them in the conformationally rigid and structurally fixed compounds. Comparison of theoretical couplings with experimental ones shows a statistically significant good to excellent agreement. A parallel analysis of the variability of the calculated values of 13C–15N spin bonds with the variability of experimental data within groups of related compounds turned out to be practically useful. The approach developed can be used to quite reasonably determine the signs of spin–spin coupling constants 13C–15N. It can also provide important additional information for assigning 13C peaks in cases where this cannot be done using standard NMR spectroscopy techniques.

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Acknowledgements

A.K.S. acknowledges Alexander von Humboldt foundation for a stipend and travel grants. The authors are thankful to Dr. D.N. Laikov for valuable discussion.

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Authors and Affiliations

  1. Department of Chemistry, Moscow State University, Moscow, 119991, Russia

    Vladislav V. Stanishevskiy & Vyacheslav A. Chertkov

  2. State Scientific Research Institute of Chemistry and Technology of Organoelement Compounds, Moscow, 105118, Russia

    Alla K. Shestakova

Authors
  1. Vladislav V. Stanishevskiy
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  2. Alla K. Shestakova
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  3. Vyacheslav A. Chertkov
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Contributions

VVS—performed analysis of the literature, optimization of geometry and quantum-chemical evaluation of spin–spin coupling constants 13C–15N for the selected compounds, prepared figures, compiled tables based on the data obtained, and also actively participated in the discussion of the results and made an oral report on this topic at the Spinus-2022 conference; AKS performed all NMR experiments and analyzed results for compound 61, participated in the discussion of the text of the manuscript, compiled Table 10, and edited the figures; VAC took an active part in the planning, writing, editing and discussion of the results, participated in statistical treatment of the result. All the authors have read and agreed to the final version of the manuscript.

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Correspondence to Vladislav V. Stanishevskiy.

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Stanishevskiy, V.V., Shestakova, A.K. & Chertkov, V.A. Analysis of 2D Maps Based on Similarity in DFT-Calculated vs Experimental 13C–15N Spin Couplings for a Representative Sample of Conformationally Rigid and Structurally Fixed Nitrogen-Containing Organic Compounds. Appl Magn Reson 53, 1693–1713 (2022). https://doi.org/10.1007/s00723-022-01503-w

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