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A crystalline monosubstituted carbene

Nature Chemistry volume 10, pages 1196–1200 (2018)Cite this article

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Abstract

By flanking a carbene carbon with two substituents, it is possible to synthesize persistent triplet carbenes and isolable singlet carbenes. Isolable singlet carbenes are among the most powerful tools in chemistry, and they have even found medicinal and materials science applications. Between the rich chemistry of disubstituted carbenes and the transient parent carbene are the monosubstituted carbenes that, so far, have only been observed in matrices at very low temperatures of just a few K. Herein, we describe the synthesis of a crystalline monosubstituted carbene. The key for isolating such a species was to design the correct substituent, namely a benzo[c]pyrrolidino heterocycle, which can single-handedly tame the intrinsic tendency of carbenes towards dimerization. The π-donor ability of the nitrogen atom, coupled with the steric bulk of chemically inert substituents at the two adjacent quaternary carbons, make these scaffolds very attractive for the isolation of a variety of other hitherto elusive electron-deficient species.

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Fig. 1: Carbenes and isolated group 15 analogues.
Fig. 2: Synthesis of the protonated carbene precursors 2a–c.
Fig. 3: Deprotonation of aldiminium salts 2a–c.
Fig. 4: Solid-state structures of 4b and 3c.
Fig. 5: Theoretical and experimental study of the electronic nature of 3c.

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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 CCDC 1814366 (2c), 1814371 (3c), 1814368 ((3c)Rh(cod)Cl), 1814370 (4b), 1835936 (5), 1814367 (7), 1814369 (8), 1814372 (9) and 1835937 (10). Copies of the data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif. All other data supporting the findings of this study are available within the article and its Supplementary Information, or from the corresponding author upon reasonable request.

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Acknowledgements

Thanks are due to the NSF (CHE-1661518) for financial support of this work, and the Japan Society for the Promotion of Science for a Postdoctoral Fellowship for Study Abroad (to R.N.). We are grateful to the W. M. Keck Foundation for funding the Keck II computer centre, and A. L. Rheingold, M. Gembicky and C. E. Moore (X-ray diffraction).

Author information

Authors and Affiliations

  1. UCSD–CNRS Joint Research Laboratory (UMI 3555), Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California, USA

    Ryo Nakano, Rodolphe Jazzar & Guy Bertrand

Authors
  1. Ryo Nakano
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  2. Rodolphe Jazzar
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  3. Guy Bertrand
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Contributions

R.N. and G.B. devised the project. All authors discussed the results and wrote the paper. R.N. performed the experimental and computational work. R.J. performed the X-ray crystallographic analyses.

Corresponding author

Correspondence to Guy Bertrand.

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The authors declare no competing interests.

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Supplementary information

Supplementary information

Synthetic procedures, physical and spectroscopic properties for all compounds described in the manuscript, a copy of their NMR spectra, crystallographic data and structure refinements for compounds 2c, 3c, (3c)Rh(cod)Cl, 4b, 5, 7, 8, 9 and 10, and the Cartesian coordinates of computational structures

Crystallographic data

CIF for compound 2c; CCDC reference: 1814366

Crystallographic data

CIF for compound 3c; CCDC reference: 1814371

Crystallographic data

CIF for compound (3c)Rh(cod)Cl; CCDC reference: 1814368

Crystallographic data

CIF for compound 4b; CCDC reference: 1814370

Crystallographic data

CIF for compound 5; CCDC reference: 1835936

Crystallographic data

CIF for compound 7; CCDC reference: 1814367

Crystallographic data

CIF for compound 8; CCDC reference: 1814369

Crystallographic data

CIF for compound 9; CCDC reference: 1814372

Crystallographic data

CIF for compound 10; CCDC reference: 1835937

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Nakano, R., Jazzar, R. & Bertrand, G. A crystalline monosubstituted carbene. Nature Chem 10, 1196–1200 (2018). https://doi.org/10.1038/s41557-018-0153-1

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