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Isolation and reactivity of an elusive diazoalkene

Nature Chemistry volume 13, pages 587–593 (2021)Cite this article

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Abstract

Most functional groups, especially those consisting of the abundant elements of organic matter—carbon, nitrogen and oxygen—have been extensively studied and only very few remain speculative due to their high intrinsic reactivity. In contrast to the well-explored chemistry of diazoalkanes (R2C=N2), diazoalkenes (R2C=C=N2) have been postulated in several organic transformations, but remain elusive long-sought intermediates. Here, we present a room-temperature stable diazoalkene, utilizing a dinitrogen transfer from nitrous oxide. This functional group shows dual-site nucleophilicity (C and N atoms) and features a bent C–C–N entity (124°) and a long N–N bond together with a remarkable low infrared absorption (1,944 cm–1). Substitution of N2 by an isocyanide leads to a vinylidene ketenimine. Furthermore, photochemically triggered loss of dinitrogen might proceed through a transient triplet vinylidene. We anticipate the existence of a stable diazoalkene functional group to pave an exciting avenue into the chemistry of low-valent carbon and unsaturated carbenes.

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Fig. 1: Diazoalkanes, carbenes, diazoalkenes, the corresponding vinylidenes and their appearance in organic reaction mechanisms.
Fig. 2: Synthesis and electronic structure of a stable diazoalkene.
Fig. 3: Computational analysis of 2 and diazoalkene derivatives.
Fig. 4: Reactivity of diazoalkene 2 towards a selection of electrophiles.
Fig. 5: The reaction between diazoalkene 2 and an ambiphilic isocyanide (Xyl = 2,6-dimethylphenyl) leads to a formal N2/isocyanide substitution to give vinylidene ketenimine 10.
Fig. 6: Irradiation of 2 with a 390 nm LED light source leads cleanly to C–H insertion product 12.

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Data availability

All data generated and analysed during this study are included in this Article and its Supplementary Information. Crystal structure data for the solid-state structures are available free of charge from the Cambridge Crystallographic Data Centre via https://www.ccdc.cam.ac.uk/structures/ under reference numbers CCDC-2013705 (2), CCDC-2013706 (3), CCDC-2013708 (4), CCDC-2013709 (5), CCDC-2043960 (6), CCDC-2043961 (7), CCDC-2043962 (9), CCDC-2043959 (10), CCDC-2013707 (12), respectively. The supplementary materials for this paper include synthetic and characterization data for all reported compounds as well as computational details.

References

  1. Curtius, T. Ueber die Einwirkung von salpetriger Säure auf salzsauren Glycocolläther. Ber. Dtsch. Chem. Ges. 16, 2230–2231 (1883).

    Article  Google Scholar 

  2. von Pechmann, H. Ueber Diazomethan. Ber. Dtsch. Chem. Ges. 27, 1888–1891 (1894).

    Article  CAS  Google Scholar 

  3. Regitz, M. & Maas, G. Diazo Compounds: Properties and Synthesis (Academic Press, 1986).

  4. Patai, S. The Chemistry of Diazonium and Diazo Groups (Wiley-VCH, 1978).

  5. Hirai, K., Itoh, T. & Tomioka, H. Persistent triplet carbenes. Chem. Rev. 109, 3275–3332 (2009).

    Article  CAS  Google Scholar 

  6. Sander, W., Bucher, G. & Wierlacher, S. Carbenes in matrixes: spectroscopy, structure, and reactivity. Chem. Rev. 93, 1583–1621 (1993).

    Article  CAS  Google Scholar 

  7. Stang, P. J. Unsaturated carbenes. Chem. Rev. 78, 383–405 (1978).

    Article  CAS  Google Scholar 

  8. Breidung, J. et al. Difluorovinylidene, F2C=C:. Angew. Chem. Int. Ed. 36, 1983–1985 (1997).

    Article  CAS  Google Scholar 

  9. Brahms, J. C. & Dailey, W. D. Difluoropropadienone as a source of difluorovinylidene and difluorodiazoethene. J. Am. Chem. Soc. 112, 4046–4047 (1990).

    Article  CAS  Google Scholar 

  10. Ervin, K. M., Ho, J. & Lineberger, W. C. A study of the singlet and triplet states of vinylidene by photoelectron spectroscopy of H2C=C−, D2C=C−, and HDC=C−. Vinylidene–acetylene isomerization. J. Chem. Phys. 91, 5974–5992 (1989).

    Article  CAS  Google Scholar 

  11. Murcko, M. A., Pollack, S. K. & Lahti, P. M. An ab initio study of diazoethene, a propadienone isoelectronic with a bent structure. J. Am. Chem. Soc. 110, 364–368 (1988).

    Article  CAS  Google Scholar 

  12. Knorr, R. Alkylidenecarbenes, alkylidenecarbenoids, and competing species: Which is responsible for vinylic nucleophilic substitution, [1 + 2] cycloadditions, 1,5-CH insertions, and the Fritsch−Buttenberg−Wiechell rearrangement? Chem. Rev. 104, 3795–3850 (2004).

    Article  CAS  Google Scholar 

  13. Seyferth, D., Hilbert, P. & Marmor, R. S. Novel diazo alkanes and the first carbene containing the dimethyl phosphite group. J. Am. Chem. Soc. 89, 4811–4812 (1967).

    Article  CAS  Google Scholar 

  14. Gilbert, J. C. & Weerasooriya, U. Diazoethenes: their attempted synthesis from aldehydes and aromatic ketones by way of the Horner-Emmons modification of the Wittig reaction. A facile synthesis of alkynes. J. Org. Chem. 47, 1837–1845 (1982).

    Article  CAS  Google Scholar 

  15. Hansmann, M. M., Antoni, P. W. & Pesch, H. Stable mesoionic N‐heterocyclic olefins (mNHOs). Angew. Chem. Int. Ed. 59, 5782–5787 (2020).

    Article  CAS  Google Scholar 

  16. Moss, R. A. Chemistry of alkanediazotates. Acc. Chem. Res. 7, 421–427 (1974).

    Article  CAS  Google Scholar 

  17. Müller, E., Ludsteck, D. & Rundel, W. Ein neuer Weg zum Diazomethan. Angew. Chem. 67, 617 (1955).

    Article  Google Scholar 

  18. Bierbaum, V. M., DePuy, C. H. & Shapiro, R. H. Gas phase reactions of anions with nitrous oxide and carbon dioxide. J. Am. Chem. Soc. 99, 5800–5802 (1977).

    Article  CAS  Google Scholar 

  19. Wislicenus, W. Synthese der Stickstoffwasserstoffsäure. Ber. Dtsch. Chem. Ges. 25, 2084–2087 (1892).

    Article  Google Scholar 

  20. Severin, K. Synthetic chemistry of nitrous oxide. Chem. Soc. Rev. 44, 6375–6386 (2015).

    Article  CAS  Google Scholar 

  21. Eymann, L. Y. M. et al. Synthesis of organic super-electron-donors by reaction of nitrous oxide with N-heterocyclic olefins. J. Am. Chem. Soc. 141, 17112–17116 (2019).

    Article  CAS  Google Scholar 

  22. Klein, S., Tonner, R. & Frenking, G. Carbodicarbenes and related divalent carbon(0) compounds. Chem. Eur. J. 16, 10160–10170 (2010).

    Article  CAS  Google Scholar 

  23. Aldeco-Perez, E. et al. Isolation of a C5-deprotonated imidazolium, a crystalline “abnormal” N-heterocyclic carbene. Science 326, 556–559 (2009).

    Article  CAS  Google Scholar 

  24. Lorberth, J. Metallorganische diazoalkane III. Diazoalkane mit germanium, blei und den iib-elementen zink, cadmium und quecksilber als substituenten. J. Organomet. Chem. 27, 303–325 (1971).

    Article  CAS  Google Scholar 

  25. Sotiropoulos, J.-M., Baceiredo, A. & Bertrand, G. Synthesis and reactivity of diazomethylenephosphoranes (P=C=N2). New phosphacumulene ylides and first stable pseudo-unsaturated diazo derivatives. J. Am. Chem. Soc. 109, 4711–4712 (1987).

    Article  CAS  Google Scholar 

  26. Baceiredo, A., R‚au, R. & Bertrand, G. Phosphorus substituted “CN2” groups: building blocks in heterocyclic chemistry. Bull. Soc. Chim. Belg. 103, 531–537 (1994).

    Article  CAS  Google Scholar 

  27. Cox, A. P., Thomas, L. F. & Sheridan, J. Microwave spectra of diazomethane and its deutero derivatives. Nature 181, 1000–1001 (1958).

    Article  CAS  Google Scholar 

  28. Liu, W. et al. Mesoionic carbene (MIC)-catalyzed H/D exchange at formyl groups. Chem 5, 2484–2494 (2019).

    Article  CAS  Google Scholar 

  29. Glendening, E. D. et al. NBO 7.0 (Theoretical Chemistry Institute, University of Wisconsin, 2018)

  30. Landis, C. R. & Weinhold, F. 3c/4e σ̂-Type long-bonding: A novel transitional motif toward the metallic delocalization limit. Inorg. Chem. 52, 5154–5166 (2013).

    Article  CAS  Google Scholar 

  31. Bott, K. Dialkylamino‐substituierte Ethylendiazoniumsalze. Chem. Ber. 120, 1867–1871 (1987).

    Article  CAS  Google Scholar 

  32. Bott, K. 2,2-(n,n′-dimethyl-ethylendiamino)-ethylendiazonium-ion, ein diazonium-ion mit ungewöhnlichen eigenschaften. Tetrahedron Lett. 26, 3199–3202 (1985).

    Article  CAS  Google Scholar 

  33. Papakondylis, A. & Mavridis, A. Electronic structure and bonding of the fastidious species CN2 and CP2: A first-principles study. J. Phys. Chem. A 123, 10290–10302 (2019).

    Article  CAS  Google Scholar 

  34. Su, M.-D. & Chuang, C.-C. Theory predicts triplet ground-state carbene containing the N-heterocyclic carbenic unit. Theor. Chem. Acc. 132, 1360 (2013).

    Article  Google Scholar 

  35. Bott, K. Alkenediazonium salts: A new chapter of classical organic chemistry. Angew. Chem. Int. Ed. 18, 259–265 (1979).

    Article  Google Scholar 

  36. Tang, C. et al. 1,1‐Hydroboration and a borane adduct of diphenyldiazomethane: A potential prelude to FLP‐N2 chemistry. Angew. Chem. Int. Ed. 56, 16588–16592 (2017).

    Article  CAS  Google Scholar 

  37. Krossing, I. & Reisinger, A. Perfluorinated alkoxyaluminate salts of cationic Brønsted acids: synthesis, structure, and characterization of [H(OEt2)2][Al{OC(CF3)3}4] and [H(THF)2][Al{OC(CF3)3}4]. Eur. J. Inorg. Chem. 2005, 1979–1989 (2005).

  38. Lucius, R., Loos, R. & Mayr, H. Key to a general concept of polar organic reactivity. Angew. Chem. Int. Ed. 41, 91–95 (2002).

    Article  CAS  Google Scholar 

  39. Bestmann, H. J., Schmid, G. & Sandmeier, D. Synthese eines stabilen Alkylidenketenimins und eines Alkylidenthioketens. Angew. Chem. 87, 34–34 (1975).

    Article  CAS  Google Scholar 

  40. Bestmann, H. J., Schmid, G. & Kumulierte Ylide, I. X. Eine neue Synthesemöglichkeit für N‐substituierte (Triphenylphosphoranyliden)ketenimine und das (Triphenylphosphoranyliden)thioketen. Chem. Ber. 113, 3369–3372 (1980).

    Article  CAS  Google Scholar 

  41. Alcarazo, M., Lehmann, C. W., Anoop, A., Thiel, W. & Fürstner, A. Coordination chemistry at carbon. Nat. Chem. 1, 295–301 (2009).

    Article  CAS  Google Scholar 

  42. Wang, Z., Herraiz, A. G., del Hoyo, A. M. & Suero, M. G. Generating carbyne equivalents with photoredox catalysis. Nature 554, 86–91 (2018).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This paper is dedicated to the memory of Manfred Regitz. This work was supported by the Fonds der Chemischen Industrie (scholarships to M.M.H. and P.W.A.), DFG (X-ray: INST 186/1324-1) and BMBF (tenure-track programme for M.M.H.). Computational resources were provided by the DFG project 405832858 and LiDO3, the high performance computing facility at TU Dortmund (DFG project 271512359). M. Alcarazo is thanked for granting access to his infrastructure at the University of Göttingen, D. Munz and F. Weinhold are acknowledged for helpful computational discussions. A. Ofial and C. Sindlinger are thanked for providing 8 and [H(Et2O)2]{Al[OC(CF3)3]4}, respectively. D.A.P. acknowledges support from the Max Planck Society. The members of the chemistry department at TU Dortmund are thanked for their support, in particular W. Hiller for the 14N and 15N NMR measurements.

Author information

Authors and Affiliations

  1. Fakultät für Chemie und Chemische Biologie, Technische Universität Dortmund, Dortmund, Germany

    P. W. Antoni, J. J. Holstein & M. M. Hansmann

  2. Georg-August Universität Göttingen, Institut für Organische und Biomolekulare Chemie, Göttingen, Germany

    P. W. Antoni, C. Golz & M. M. Hansmann

  3. Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, Mülheim an der Ruhr, Germany

    D. A. Pantazis

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Contributions

All experiments were conducted by M.M.H. (initial discovery) and P.W.A. Crystallographic analyses of borane adducts 4 and 5 were performed by J.J.H. and C.G. measured and refined the remaining solid-state structures. DFT, NBO and NRT calculations were performed by M.M.H. and MP2, CASSCF, NEVPT2 and CCSD(T) calculations were performed by D.A.P. The project was designed and coordinated by M.M.H who also wrote the manuscript.

Corresponding author

Correspondence to M. M. Hansmann.

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The authors declare no competing interests.

Additional information

Peer review information Nature Chemistry thanks Peter Schreiner 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 data, synthesis and characterization data, NMR spectra, X-ray crystallographic data, computational details, Supplementary figures and tables.

Supplementary Data 1

Crystallographic data for compound 2. CCDC reference 2013705.

Supplementary Data 2

Crystallographic data for compound 3. CCDC reference 2013706.

Supplementary Data 3

Crystallographic data for compound 4. CCDC reference 2013708.

Supplementary Data 4

Crystallographic data for compound 5. CCDC reference 2013709.

Supplementary Data 5

Crystallographic data for compound 6. CCDC reference 2043960.

Supplementary Data 6

Crystallographic data for compound 7. CCDC reference 2043961.

Supplementary Data 7

Crystallographic data for compound 9. CCDC reference 2043962.

Supplementary Data 8

Crystallographic data for compound 10. CCDC reference 2043959.

Supplementary Data 9

Crystallographic data for compound 12. CCDC reference 2013707.

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Antoni, P.W., Golz, C., Holstein, J.J. et al. Isolation and reactivity of an elusive diazoalkene. Nat. Chem. 13, 587–593 (2021). https://doi.org/10.1038/s41557-021-00675-5

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