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Direct conversion of white phosphorus to versatile phosphorus transfer reagents via oxidative onioation

Nature Chemistry volume 14, pages 384–391 (2022)Cite this article

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Abstract

The main feedstock for the value-added phosphorus chemicals used in industry and research is white phosphorus (P4), from which the key intermediate for forming P(III) compounds is PCl3. Owing to its high reactivity, syntheses based on PCl3 are often accompanied by product mixtures and laborious work-up procedures, so an alternative process to form a viable P(III) transfer reagent is desirable. Our concept of oxidative onioation, where white phosphorus is selectively converted into triflate salts of versatile P1 transfer reagents such as [P(LN)3][OTf]3 (LN is a cationic, N-based substituent; that is, 4-dimethylaminopyridinio), provides a convenient alternative for the implementation of P–O, P–N and P–C bonds while circumventing the use of PCl3. We use p-block element compounds of type RnE (for example, Ph3As or PhI) to access weak adducts between nitrogen Lewis bases LN and the corresponding dications [RnELN]2+. The proposed equilibrium between [RnELN]2+ + LN and [RnE(LN)2]2+ allows for the complete oxidative onioation of all six P–P bonds in P4 to yield highly reactive and versatile trications [P(LN)3]3+.

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Fig. 1: Routes into value-added phosphorus chemicals from phosphate rock.
Fig. 2: Formation of butterfly compound 3[OTf]2 via oxidative onioation of P4.
Fig. 3: Onio-ligand-assisted deoxygenation reactions of compounds Ph3AsO and PhIO.
Fig. 4: Selective oxidative onioation of white phosphorus (P4) to P1 transfer reagents.
Fig. 5: Mechanistic investigation of the successive degradation of white phosphorus with weak adduct 5[OTf]2.
Fig. 6: Application of 11[OTf]3 as an alternative to PCl3 in P–O, P–N and P–C bond-formation reactions.

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Data availability

The data supporting the findings of this study are available within the paper and its Supplementary Information. All structures have been deposited with the Cambridge Crystallographic Data Centre (CCDC) and can be accessed free of charge via http://www.ccdc.cam.ac.uk/data_request/cif under the numbers 2105521 (2[OTf]2), 2019149 (5[OTf]2·CH2Cl2), 2105523 (5[BArF]2), 2019148 (6[OTf]2), 2019145 (7[OTf]2), 2019147 (11[OTf]3·CH2Cl2), 2061965 (12[OTf]·0.67 MeNO2), 2105520 ((LN)2POP(LN)2[OTf]4·4 CH3CN), 2019146 (14[OTf]3·2 CH3CN) and 2061966 (24g).

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Acknowledgements

We thank the European Research Council (ERC starting grant, SynPhos-307616), the German Science foundation (WE 4621/6-1) and TU Dresden for financial support. A.B. and A.F. thank MICIU/AEI of Spain (project no. PID2020-115637GB-I00, FEDER funds) for financial support. We thank S. Albrecht for alcoholysis reactions and P. Lange for experimental assistance and elemental analysis measurements. We also thank N. Rae Brindle for helpful discussions. Solvay Chemicals is gratefully acknowledged for their donation of the chemicals Me3SiOTf and Tf2O.

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Author notes

  1. These authors contributed equally: M. Donath, K. Schwedtmann.

Authors and Affiliations

  1. Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, Dresden, Germany

    Maximilian Donath, Kai Schwedtmann, Tobias Schneider, Felix Hennersdorf & Jan J. Weigand

  2. Department of Chemistry, Universitat de les Illes Balears, Palma de Mallorca, Spain

    Antonio Bauzá & Antonio Frontera

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Contributions

M.D., K.S. and J.J.W. developed the oxidative onioation procedures, developed the initial procedures for formation of the final products and performed mechanistic studies. M.D., K.S. and T.S. optimized the synthesis, isolation and purifications of products from P1 synthons. A.B. and A.F. performed the quantum chemical calculations. F.H. and J.J.W. were responsible for collecting X-ray data and refinement. K.S. and J.J.W. prepared the manuscript. K.S. and J.J.W. conceived, oversaw and directed the project. All authors discussed the results and commented on the manuscript.

Corresponding author

Correspondence to Jan J. Weigand.

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Extended data

Extended Data Fig. 1 31P NMR spectra of the reaction of P4 with 1 equiv. of 22+ as either OTf– or BArF– salt.

a, 31P NMR spectrum (CH3CN, C6D6-capillary, 300 K) of the reaction of P4 with 2[OTf]2 showing resonances for P4 and butterfly compound 32+ (δ(PA) = –327.6 ppm, δ(PX) = –174.9 ppm); b, 31P NMR spectrum (CH3CN / CH2Cl2, C6D6-capillary, 300 K) of the reaction of P4 with 2[BArF]2 showing resonances for P4 and trace amounts of 32+ (δ(PA) = –328.3 ppm, δ(PX) = –175.1 ppm).

Extended Data Fig. 2 Complementary DFT investigations regarding the equilibrium between Ph3As(Quin)2+ (72+) and Ph3As(Quin)(OTf)+ (8+).

a, Optimized geometries and energy difference for Ph3As(Quin)(OTf)+ and Ph3As(Quin)2+; b, Results of the thermochemical calculations on the equilibrium between quinoline, Ph3As(OTf)2 and Ph3As(Quin)(OTf)+ (BP86-D3/def2-TZVP level of theory); Quin = quinoline.

Extended Data Fig. 3 Molecular structures of tetracation (LN)2POP(LN)24+ (LN = DMAP) in (LN)2POP(LN)2[OTf]4 ∙ 4 CH3CN.

Thermal ellipsoids are displayed at 50% probability level and hydrogen atoms and counterions are omitted for clarity.

Extended Data Fig. 4 Compounds being formed in the degradation of P4.

a, Structures are derived from the obtained resonances in the 31P NMR spectra (b) of the reaction of P4 with an excess of oxidant 2[OTf]2 and varying amounts of DMAP (LN).

Extended Data Fig. 5 Optimized geometries and energy differences of the proposed intermediates in the mechanism of the successive degradation of P4 with Ph3As(LN)2[OTf]2 (5[OTf]2, LN = DMAP).

Computed on BP86-D3/def2-TZVP level of theory; overall Gibb’s energy ΔG = –30.9 kcal/mol. Energies in dichloromethane.

Supplementary information

Supplementary Information

Materials and methods, synthesis and procedures, characterization data, NMR spectra, crystallographic data, DFT calculation data, references, Figs. 1–74, Tables 1–3 and Schemes 1 and 2.

Supplementary Data 1

Crystallographic data for compound 2[OTf]2; CCDC reference 2105521.

Supplementary Data 2

Crystallographic data for compound 5[OTf]2; CCDC reference 2105520.

Supplementary Data 3

Crystallographic data for compound 5[BArF]2; CCDC reference 2105523.

Supplementary Data 4

Crystallographic data for compound 6[OTf]2; CCDC reference 2019148.

Supplementary Data 5

Crystallographic data for compound 7[OTf]2; CCDC reference 2019145.

Supplementary Data 6

Crystallographic data for compound 11[OTf]3; CCDC reference 2019147.

Supplementary Data 7

Crystallographic data for compound 12[OTf]; CCDC reference 2061965.

Supplementary Data 8

Crystallographic data for compound (LN)2POP(LN)2[OTf]4; CCDC reference 2105520.

Supplementary Data 9

Crystallographic data for compound 14[OTf]3; CCDC reference 2019146.

Supplementary Data 10

Crystallographic data for compound 24g; CCDC reference 2061966.

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Donath, M., Schwedtmann, K., Schneider, T. et al. Direct conversion of white phosphorus to versatile phosphorus transfer reagents via oxidative onioation. Nat. Chem. 14, 384–391 (2022). https://doi.org/10.1038/s41557-022-00913-4

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