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Hydrogen splitting at a single phosphorus centre and its use for hydrogenation

Nature Chemistry (2024)Cite this article

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Abstract

Catalytic processes are largely dominated by transition-metal complexes. Main-group compounds that can mimic the behaviour of the transition-metal complexes are of great interest due to their potential to substitute or complement transition metals in catalysis. While a few main-group molecular centres were shown to activate dihydrogen via the oxidative addition process, catalytic hydrogenation using these species has remained challenging. Here we report the synthesis, isolation and full characterization of the geometrically constrained phosphenium cation with the 2,6-bis(o-carborano)pyridine pincer-type ligand. Notably, this cation can activate the H–H bond by oxidative addition to a single PIII cationic centre, producing a dihydrophosphonium cation. This phosphenium cation is also capable of catalysing hydrogenation reactions of C=C double bonds and fused aromatic systems, making it a main-group compound that can both activate H2 at a single molecular main-group centre and be used for catalytic hydrogenation. This finding shows the potential of main-group compounds, in particular phosphorus-based compounds, to serve as metallomimetic hydrogenation catalysts.

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Fig. 1: Synthesis and structures of 1-Cl, 1-OTf and [1+][B(C6F5)4].
Fig. 2: Electronic structure of 1+.
Fig. 3: Activation of H2 by 1+.
Fig. 4: Catalysis with [1+][B(C6F5)4].
Fig. 5: Mechanism of the catalysis.
Fig. 6: Computed hydrogenation mechanism.

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Data availability

The data supporting the findings of this study are available within the paper and its Supplementary Information (experimental procedures, DFT calculations and characterization data). X-ray data are available free of charge from the Cambridge Crystallographic Data Centre under references CCDC-2267545 (1-Cl), CCDC-2267548 (1-OTf), CCDC-2267547 ([1+][B(C6F5)4]) and CCDC-2267546 ([1+-H2][B(C6F5)4]). These data can be obtained free of charge from The Cambridge Crystallographic Data Centre (www.ccdc.cam.ac.uk/data_request/cif). The Cartesian coordinates and energies of all optimized molecules are provided as *.xyz files.

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Acknowledgements

This work was supported by the Israeli Science Foundation, grant 195/22, the Israel Ministry of Science Technology & Space, grant 01032376, and the US–Israel Binational Science Foundation, grant 2018221. D.T. thanks the Ariane de Rothschild Women Doctoral scholarship for outstanding female PhD students.

Author information

Author notes

  1. These authors contributed equally: Deependra Bawari, Donia Toami, Kuldeep Jaiswal.

Authors and Affiliations

  1. School of Chemistry, Raymond and Beverly Sackler Faculty of Exact Sciences, Tel Aviv University, Tel Aviv, Israel

    Deependra Bawari, Donia Toami, Kuldeep Jaiswal & Roman Dobrovetsky

Authors
  1. Deependra Bawari
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  2. Donia Toami
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Contributions

D.B., D.T. and K.J. performed all the synthetic work. D.B. analysed and solved all X-ray molecular structures and did all the computational studies. R.D. supervised the project and wrote the paper with input from all authors.

Corresponding author

Correspondence to Roman Dobrovetsky.

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The authors declare no competing interests.

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Nature Chemistry thanks Josh Abbenseth, Shigeyoshi Inoue and the other, anonymous, reviewer for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary discussion and Figs. 1–76.

Supplementary Data 1

The Cartesian coordinates and energies of all optimized molecules are provided as *.xyz files.

Supplementary Data 2

Crystallographic data for compound 1-Cl; CCDC reference 2267545.

Supplementary Data 3

Structure parameters file for compound 1-Cl. CCDC reference 2267545.

Supplementary Data 4

Crystallographic data for compound 1-OTf; CCDC reference 2267548.

Supplementary Data 5

Structure parameters file for compound 1-OTf. CCDC reference 2267548.

Supplementary Data 6

Crystallographic data for compound [1+][B(C6F5)4]; CCDC reference 2267547.

Supplementary Data 7

Structure parameters file for compound [1+][B(C6F5)4]. CCDC reference 2267547.

Supplementary Data 8

Crystallographic data for compound [1+-H2][B(C6F5)4]; CCDC reference 2267546.

Supplementary Data 9

Structure parameters file for compound [1+-H2][B(C6F5)4]. CCDC reference 2267546.

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Bawari, D., Toami, D., Jaiswal, K. et al. Hydrogen splitting at a single phosphorus centre and its use for hydrogenation. Nat. Chem. (2024). https://doi.org/10.1038/s41557-024-01569-y

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