Ortho-phosphite (PO33−): Mechanochemical Synthesis of a Missing Oxoanion and Precursor to Value-Added Organophosphorus Compounds
Name
ortho-phosphite-(po33-)-mechanochemical-synthesis-of-a-missing-oxoanion-and-precursor-to-value-added-organophosphorus.pdf
Description
Published version
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3.27 MB
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Checksum (MD5)
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Author(s)
Löwe, Pawel
Taakili, Rachid
Xin, Tiansi
Haldar, Hritwik
Herzog, Antonia
Shao-Horn, Yang
Cummins, Christopher C
Date Issued
November 26, 2025
Journal
ACS Central Science
Publisher
American Chemical Society
Citation
Ortho-phosphite (PO33−): Mechanochemical Synthesis of a Missing Oxoanion and Precursor to Value-Added Organophosphorus Compounds. Pawel Löwe, Rachid Taakili, Tiansi Xin, Hritwik Haldar, Antonia Herzog, Yang Shao-Horn, and Christopher C. Cummins. ACS Central Science 2026 12 (1), 40-48.
Version
Final published version
Abstract
Despite the ubiquity of the well-known phosphorus polyanion phosphite
(HPO2−3)
, it appears to be the case that no simple salt of the corresponding conjugate base
(PO3−3
, “ortho-phosphite”) has ever been reported. We report the synthesis and characterization of this elusive species as a major component of a mixture obtained upon mechanochemical reduction of condensed phosphates, as evidenced by solid-state 31P NMR and Raman spectroscopy as well as subsequent reactivity studies. To corroborate the 31P NMR spectroscopic assignment, we independently generated Na3PO3 and K3PO3 by deprotonation of Na2HPO3 with NaCH2SiMe3 and of K2HPO3 with KCH2Ph, respectively, providing an orthogonal route to
PO3−3
salts whose spectroscopic signatures match those observed in the mixture obtained by mechanochemical reduction. We further found that ortho-phosphite can act as a precursor for various phosphorus chemicals, such as P(OSiMe3)3 (46%), which is already well established as a precursor to a plethora of useful organophosphorus compounds. Therefore, our results not only establish the first formal pathway from P(V) phosphate starting materials to P(OSiMe3)3 without the intermediacy of white phosphorus, but also open the door to a broad range of downstream transformations based on this sustainable pathway. Additionally, BaHPO3·H2O (66%), OP(OMe)2Me (DMMP), and OP(OBn)2Bn (DBBP) have been generated directly from ortho-phosphite, all traditionally synthesized from white phosphorus.
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DOI of Published Version
https://doi.org/10.1021/acscentsci.5c01595
