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White phosphorus first

Nature Chemistry volume 14, pages 362–364 (2022)Cite this article

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Many of the methods used to make phosphines proceed via phosphorus trichloride-based intermediates, leading to chloride waste that is difficult to recycle. It has now been shown that this disadvantage can be overcome by using a method that directly converts white phosphorus into value-added phosphorus compounds.

The annual production of elemental white phosphorus, P4, amounts to ∼1 million tons per year and requires the reduction of phosphate, which is an immensely energy-consuming process. White phosphorus is a highly valuable product from which all organophosphorus compounds (OPCs) are currently prepared. Making the best possible use of it is of central concern in modern sustainable phosphorus chemistry1. Most industrially relevant OPCs contain only one phosphorus atom, meaning that the six P–P bonds in P4 must be broken to obtain useful P1 building blocks. On a large scale this is currently achieved oxidatively by reaction2 of P4 with chlorine gas to give PCl3 or PCl5, or by acid-catalysed disproportion3 (2P4 + 12H2O + H+ → 5PH3 + 3H3PO4 + H+) to produce PH3. Subsequent reactions of PCln with nucleophiles produce large amounts of chloride salts, which need laborious and costly recycling4. In this respect, PH3 performs better because it allows — at least in principle — the hydrophosphination of unsaturated reagents according to PH3 + 3A=B → P(A–BH)3, making the reaction atom-efficient. But PH3 is a very toxic pyrophoric chemical reagent that is only produced in 62% yield in the process described above and, in many cases, this reaction is not as straightforward in practice as it may seem.

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Fig. 1: Direction conversion of white phosphorus into value-added phosphorus compounds.

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  1. Department of Chemistry and Applied Bioscience, ETH Zürich, Zürich, Switzerland

    Hansjörg Grützmacher

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Grützmacher, H. White phosphorus first. Nat. Chem. 14, 362–364 (2022). https://doi.org/10.1038/s41557-022-00921-4

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