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Isolation and characterization of diazoolefins

Nature Chemistry volume 13, pages 1055–1060 (2021)Cite this article

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Abstract

Diazoolefins tend to be highly reactive compounds that rapidly lose dinitrogen. So far, most experimental evidence for diazoolefins is indirect, via trapping experiments. Here we show that diazoolefins are observed to form in reactions of N-heterocyclic olefins with nitrous oxide. The products benefit from resonance stabilization, which enables isolation on a preparative scale, and comprehensive characterization, which includes crystallographic analyses. N-heterocyclic diazoolefins show a strong ylidic character, with a high charge density at the carbon atom next to the diazo group. Despite the presence of terminal N2 groups, N-heterocyclic diazoolefins display a good thermal stability, which surpasses that observed for most diazoalkanes. N-heterocyclic diazoolefins can bind transition and main group metal complexes without the liberation of dinitrogen, and spectroscopic data show that they are strong electron donors. They can also undergo reactions that involve the N2 group, as evidenced by cycloaddition reactions.

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Fig. 1: Properties and structures of diazoolefins and related compounds.
Fig. 2: Electronic structure of diazoolefins.
Fig. 3: Photoreactions of diazoolefins.
Fig. 4: Synthesis of diazoolefin complexes.
Fig. 5: Synthesis of organic diazoolefin adducts.

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Data availability

Crystallographic data for the structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers 2059964 (1), 2059969 (3), 2081293 (4), 2084389 (7), 2059970 (8), 2059965 (9), 2059966 (10), 2059971 (11), 2059972 (12), 2082844 (13), 2059967 (14), 2059973 (15), 2059968 (16) and 2059974 (17). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. Relevant data for this study are available within the article and its Supplementary Information. Original data files for the spectroscopic analyses can be obtained from the authors upon reasonable request.

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Acknowledgements

This work was supported by funding from the EPFL. We thank A. Gitlina for the infrared spectroscopy measurements, W. Feuerstein for help with the synthesis of 1, C. Berton for help with NMR analyses and D. Ortiz for help with mass spectrometry.

Author information

Authors and Affiliations

  1. Institut des Sciences et Ingénierie Chimiques, École Polytechnique Fédérale de Lausanne (EPFL), Lausanne, Switzerland

    Paul Varava, Zhaowen Dong, Rosario Scopelliti, Farzaneh Fadaei-Tirani & Kay Severin

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  1. Paul Varava
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Contributions

P.V. and K.S. designed the experiments, P.V. performed the synthetic experiments and analysed the data, Z.D. performed the computational analysis, R.S. and F.F.-T. collected and processed the X-ray data, and P.V., Z.D. and K.S. co-wrote the manuscript. All the authors discussed the results and commented on the manuscript.

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Correspondence to Kay Severin.

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The authors declare no competing interests.

Additional information

Peer review information Nature Chemistry thanks Gabriela Borosky, Tiow-Gan Ong and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Experimental procedures, analytical data including copies of NMR spectra, and details regarding the crystallographic and computational analyses.

Supplementary Data 1

Crystallographic data for compound 1; CCDC reference 2059964.

Supplementary Data 2

Crystallographic data for compound 3; CCDC reference 2059969.

Supplementary Data 3

Crystallographic data for compound 4; CCDC reference 2081293.

Supplementary Data 4

Crystallographic data for compound 7; CCDC reference 2084389.

Supplementary Data 5

Crystallographic data for compound 8; CCDC reference 2059970.

Supplementary Data 6

Crystallographic data for compound 9; CCDC reference 2059965.

Supplementary Data 7

Crystallographic data for compound 10; CCDC reference 2059966.

Supplementary Data 8

Crystallographic data for compound 11; CCDC reference 2059971.

Supplementary Data 9

Crystallographic data for compound 12; CCDC reference 2059972.

Supplementary Data 10

Crystallographic data for compound 13; CCDC reference 2082844.

Supplementary Data 11

Crystallographic data for compound 14; CCDC reference 2059967.

Supplementary Data 12

Crystallographic data for compound 15; CCDC reference 2059973.

Supplementary Data 13

Crystallographic data for compound 16; CCDC reference 2059968.

Supplementary Data 14

Crystallographic data for compound 17; CCDC reference 2059974.

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Varava, P., Dong, Z., Scopelliti, R. et al. Isolation and characterization of diazoolefins. Nat. Chem. 13, 1055–1060 (2021). https://doi.org/10.1038/s41557-021-00790-3

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