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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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).
Schipper, W. Phosphorus: too big to fail. Eur. J. Inorg. Chem. 2014, 1567–1571 (2014).
Emsley, J. The 13th Element: The Sordid Tale of Murder, Fire and Phosphorus (Wiley, 2000).
Diskowski, H. & Hofmann T. in Ullmann’s Encyclopedia of Industrial Chemistry 6th edn (Wiley, 2002).
Schrödter, K., Bettermann, G., Staffel, T., Klein, T. & Hofmann, T. in Ullmann’s Encyclopedia of Industrial Chemistry 6th edn (Wiley, 2002).
Withers, P. J. A. et al. Greening the global phosphorus cycle: how green chemistry can help achieve planetary P sustainability. Green Chem. 17, 2087–2099 (2015).
Jupp, A. R., Beijert, S., Narain, G. C., Schipper, W. & Slootweg, J. C. Phosphorus recovery and recycling—closing the loop. Chem. Soc. Rev. 50, 87–101 (2021).
Cossairt, B. M., Piro, N. A. & Cummins, C. C. Early-transition-metal-mediated activation and transformation of white phosphorus. Chem. Rev. 110, 4164–4177 (2010).
Caporali, M., Gonsalvi, L., Rossin, A. & Peruzzini, M. P4 activation by late-transition metal complexes. Chem. Rev. 110, 4178–4235 (2010).
Hoidn, C. M., Scott, D. J. & Wolf, R. Transition-metal-mediated functionalization of white phosphorus. Chem. Eur. J. 27, 1886–1902 (2021).
Scheer, M., Balazs, G. B. & Seitz, A. P4 activation by main group elements and compounds. Chem. Rev. 110, 4236–4256 (2010).
Giffin, N. A. & Masuda, J. D. Reactivity of white phosphorus with compounds of the p-block. Coord. Chem. Rev. 255, 1342–1359 (2011).
Holthausen, M. & Weigand, J. J. The chemistry of cationic polyphosphorus cages—syntheses, structure and reactivity. Chem. Soc. Rev. 43, 6639–6675 (2014).
Borger, J. E., Ehlers, A. W., Slootweg, J. C. & Lammertsma, K. Functionalization of P4 through direct P-C bond formation. Chem. Eur. J. 23, 11738–11746 (2017).
Gantner, O., Schipper, W. & Weigand J. J. Sustainable Phosphorus Management 1st edn (Springer, 2014).
Lennert, U. et al. Directs catalytic transformation of white phosphorus into arylphosphines and phosphonium salts. Nat. Catal. 2, 1101–1106 (2019).
Scott, D. J., Cammarata, J., Schimpf, M. & Wolf, R. Synthesis of monophosphines directly from white phosphorus. Nat. Chem. 13, 458–464 (2021).
Schoemaker, R., Schwedtmann, K. & Weigand, J. J. Pyrazolyl-substituted phosphorus(III) compounds in synthesis. Coord. Chem. Rev. 436, 213829 (2021).
Feldmann, K.-O., Fröhlich, R. & Weigand, J. J. Access to catenated and branched polyphosphorus ligands and coordination complexes via a tri(pyrazolyl)phosphane. Chem. Commun. 48, 4296–4298 (2012).
Feldmann, K.-O. & Weigand, J. J. P-N/P-P bond metathesis for the synthesis of complex polyphosphanes. J. Am. Chem. Soc. 134, 15443–15456 (2012).
Schoemaker, R. et al. Controlled scrambling reactions to polyphosphanes via bond metathesis reactions. Chem. Sci. 10, 11054–11063 (2019).
Taube, C. et al. P-P condensation and P-N/P-P bond metathesis: facile synthesis of cationic tri- and tetraphosphanes. Angew. Chem. Int. Ed. 59, 3585–3591 (2020).
Weigand, J. J., Feldmann, K.-O., Echterhoff, A. K. C., Ehlers, A. & Lammertsma, K. Preparation of ligand-stabilized [P4O4]2+ by controlled hydrolysis of a Janus head type diphosphorus trication. Angew. Chem. Int. Ed. 49, 6178–6181 (2010).
Feldmann, K.-O., Schulz, S., Klotter, F. & Weigand, J. J. A versatile protocol for the quantitative and smooth conversion of phosphane oxides into synthetically useful pyrazolylphosphonium salts. ChemSusChem 4, 1805–1812 (2011).
Echterhoff, A. K. C., Yogendra, S., Kösters, J., Fischer, R. & Weigand, J. J. A versatile protocol for the synthesis of pyrazolyl-substituted pyridinium and guanidinium salts from pyridone and urea derivatives. Eur. J. Org. Chem. 34, 7631–7642 (2014).
Weiss, R., Salomon, N. J., Miess, G. E. & Roth, R. Poly-onio-substituted quinones as strong electron acceptors. Angew. Chem. Int. Ed. 25, 917–919 (1986).
Weiss, R. & Engel, S. Poly-oÿnio substituted phosphorus compounds. Synthesis 1991, 1077–1079 (1991).
Schorpp, M. et al. Synthesis and application of a perfluorinated ammoniumyl radical cation as a very strong deelectronator. Angew. Chem. Int. Ed. 59, 9453–9459 (2020).
Geeson, M. B. & Cummins, C. C. Phosphoric acid as precursor to chemicals traditionally synthesized from white phosphorus. Science 359, 1383–1385 (2018).
Geeson, M. B. & Cummins, C. C. Let’s make white phosphorus obsolete. ACS Cent. Sci. 6, 848–860 (2020).
Chitnis, S. S. et al. Bipyridine complexes of E3+ (E = P, As, Sb, Bi): strong Lewis acids, sources of E(OTf)3 and synthons for EI and EV cations. Chem. Sci. 6, 6545–6555 (2015).
Donath, M., Bodensteiner, M. & Weigand, J. J. Versatile reagent Ph3As(OTf)2: one-pot synthesis of [P7(AsPh3)3][OTf]3 from PCl3. Chem. Eur. J. 20, 17306–17310 (2014).
Robertson, A. P. M. et al. Establishing the coordination chemistry of antimony(V) cations: systematic assessment of Ph4Sb(OTf) and Ph3Sb(OTf)2 as Lewis acceptors. Chem. Eur. J. 21, 7902–7913 (2015).
Donath, M. et al. Ligand-stabilized [P4]2+ cations. Angew. Chem. Int. Ed. 51, 2964–2967 (2012).
Sapsford, J. S. et al. Establishing the role of triflate anions in H2 activation by a cationic triorganotin(IV) Lewis acid. ACS Catal. 10, 7573–7583 (2020).
Scott, D. A. et al. Versatile catalytic hydrogenation using a simple tin(IV) Lewis acid. Angew. Chem. Int. Ed. 55, 14738–14742 (2016).
Woessner, D. E. Brownian motion and its effects in NMR chemical exchange and relaxation in liquids. Concept Magnetic Res. 8, 397–442 (1996).
Becke, A. D. Density-functional exchange-energy approximation with correct asymptotic behavior. Phys. Rev. A 38, 3098 (1988).
Perdew, J. P. Erratum: density-functional approximation for the correlation energy of the inhomogeneous electron gas. Phys. Rev. B 34, 7406 (1986).
Perdew, J. P. Density-functional approximation for the correlation energy of the inhomogeneous electron gas. Phys. Rev. B 33, 8822 (1986).
Grimme, S., Antony, J., Ehrlich, S. & Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 132, 154104–154119 (2010).
Weigend, F. & Ahlrichs, R. Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: design and assessment of accuaracy. Phys. Chem. Chem. Phys. 7, 3297–3305 (2005).
Mo, H., Wang, A., Wilkinson, P. S. & Pochapsky, T. C. Closed-shell ion pairs: cation and aggregate dynamics of tetraalkylammonium salts in an ion-pairing solvent. J. Am. Chem. Soc. 119, 11666–11673 (1997).
Marcus, Y. Electrostriction, ion solvation, and solvent release on ion pairing. J. Phys. Chem. B 109, 18541–18549 (2005).
Hendrickson, J. B. in Encyclopaedia of Reagents for Organic Synthesis Vol. 8 (ed. Paquette, L. A.) 5405–5407 (Wiley, 1995).
Hendrickson, J. B. & Hussoin, Md. S. Reactions of carboxylic acids with phosphonium anhydrides. J. Org. Chem. 52, 4137–4139 (1987).
Rovnaník, P., Kapička, L., Taraba, J. & Černík, M. Base-induced dismutation of POCl3 and POBr3: synthesis of ligand-stabilized dioxophosphonium cations. Inorg. Chem. 43, 2435–2442 (2004).
Foris, A. 19F and 1H NMR spectra of halocarbons. Magn. Reson. Chem. 42, 534–555 (2004).
Weiss, R. & Seubert, J. Electrostatic activation of hypervalent organo-iodine compounds: bis(onio)-substituted aryliodine(III) salts. Angew. Chem. Int. Ed. 33, 891–893 (1994).
Weigand, J. J. & Burford, N. in Comprehensive Inorganic Chemistry II: From Elements to Applications (eds Reedijk, J. & Poeppelmeier, K.) 119–149 (Elsevier, 2013).
Pommer, H. The Wittig reaction in industrial practice. Angew. Chem. Int. Ed. 16, 423–429 (1977).
Bertau, M., Müller, A., Fröhlich, P. & Katzberg, M. Industrielle Anorganische Chemie 4th edn (Wiley, 2013).
Corbridge, D. E. C. Phosphorus: Chemistry, Biochemistry and Technology 6th edn (CRC Press, 2013).
Fest, C. & Schmidt, K.-J. Chemie der Pflanzenschutz- und Schädlingsbekämpfungsmittel Vol. 1. (Springer, 1970).
Dill, G. M. et al. Glyphosate: Discovery, Development, Applications, and Properties (Wiley, 2000).
Panzer, R. et al. Versatile tri(pyrazolyl)phosphanes as precursor for the synthesis of highly emitting InP/ZnS quantum dots. Angew. Chem. Int. Ed. 56, 14737–14742 (2017).
Guo, H., Fan, Y. C., Sun, Z., Wu, Y. & Kwon, O. Phosphine organocatalysis. Chem. Rev. 118, 10049–10293 (2018).
Levason, W. in Organophosphorus Compounds (ed. Hartley, F. R.) Ch. 15, 567–641 (Wiley, 1990).
Maryanoff, B. E. & Reitz, A. B. The Wittig olefination reaction and modifications involving phosphoryl-stabilized carbanions. Stereochemistry, mechanism, and selected synthetic aspects. Chem. Rev. 89, 863–927 (1989).
Leutkens, M. L. Jr, Sattelberger, A. P., Murray, H. H., Basil, J. D. & Fackler, J. P. Jr. in Inorganic Syntheses (ed. Angelici, R. J.) Ch. 8, 305–310 (Wiley, 1990).
Chaloux, B. L. et al. P(CN)3 precursor for carbon phosphonitride extended solids. Chem. Mater. 27, 4507–4510 (2015).
Weiss, R. & Engel, S. Electrostatic activation of nucleofuges: cationic leaving groups. Angew. Chem. Int. Ed. 31, 216–217 (1992).
Hengfeld, A. & Nast, R. CC Streckfrequenzen und δ31P-Werte der Phosphane P(CCC6H5)n(C6H5)3-n. Chem. Ber. 116, 2035–2036 (1983).
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.
The authors declare no competing interests.
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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.
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.
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.
Crystallographic data for compound 2[OTf]2; CCDC reference 2105521.
Crystallographic data for compound 5[OTf]2; CCDC reference 2105520.
Crystallographic data for compound 5[BArF]2; CCDC reference 2105523.
Crystallographic data for compound 6[OTf]2; CCDC reference 2019148.
Crystallographic data for compound 7[OTf]2; CCDC reference 2019145.
Crystallographic data for compound 11[OTf]3; CCDC reference 2019147.
Crystallographic data for compound 12[OTf]; CCDC reference 2061965.
Crystallographic data for compound (LN)2POP(LN)2[OTf]4; CCDC reference 2105520.
Crystallographic data for compound 14[OTf]3; CCDC reference 2019146.
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