Sustainable Production of Reduced Phosphorus Compounds: Mechanochemical Hydride Phosphorylation Using Condensed Phosphates as a Route to Phosphite
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acscentsci.1c01381.pdf
Description
Published version
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2.12 MB
Format
Adobe PDF
Checksum (MD5)
e14123538b4bf9406a964c36c448d1e0
Author(s)
Zhai, Feng
Xin, Tiansi
Geeson, Michael B
Cummins, Christopher C
Date Issued
2022
Journal
ACS Central Science
Publisher
American Chemical Society (ACS)
Citation
Zhai, Feng, Xin, Tiansi, Geeson, Michael B and Cummins, Christopher C. 2022. "Sustainable Production of Reduced Phosphorus Compounds: Mechanochemical Hydride Phosphorylation Using Condensed Phosphates as a Route to Phosphite." ACS Central Science, 8 (3).
Version
Final published version
Abstract
In pursuit of a more sustainable production of phosphorous acid (H3PO3), a versatile chemical with phosphorus in the +3 oxidation state, we herein report that condensed phosphates can be employed to phosphorylate hydride reagents under solvent-free mechanochemical conditions to furnish phosphite (HPO3 2-). Using potassium hydride as the hydride source, sodium trimetaphosphate (Na3P3O9), triphosphate (Na5P3O10), pyrophosphate (Na4P2O7), fluorophosphate (Na2PO3F), and polyphosphate ("(NaPO3) n ") engendered phosphite in optimized yields of 44, 58, 44, 84, and 55% based on total P content, respectively. Formation of overreduced products including hypophosphite (H2PO2 -) was identified as a competing process, and mechanistic investigations revealed that hydride attack on in-situ-generated phosphorylated phosphite species is a potent pathway for overreduction. The phosphite generated from our method was easily isolated in the form of barium phosphite, a useful intermediate for production of phosphorous acid. This method circumvents the need to pass through white phosphorus (P4) as a high-energy intermediate and mitigates involvement of environmentally hazardous chemicals. A bioproduced polyphosphate was found to be a viable starting material for the production of phosphite. These results demonstrate the possibility of accessing reduced phosphorus compounds in a more sustainable manner and, more importantly, a means to close the modern phosphorus cycle.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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Creative Commons Attribution-NonCommercial-NoDerivs License
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DOI of Published Version
https://doi.org/10.1021/ACSCENTSCI.1C01381
