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Updated: Jul 18, 2025

Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of PhosphorusI
Published on: November 22, 2016
Understanding Reactive Sulfur Species through P/S Synergy
Michael M Wade Wolfe1, Michael D Pluth1
1Department of Chemistry and Biochemistry, Materials Science Institute, Knight Campus for Accelerating Scientific Impart, and Institute of Molecular Biology, University of Oregon, Eugene, Oregon, 97403-1253, United States.
Abstract:
We investigated the differential oxidative and nucleophilic chemistry of reactive sulfur and oxygen anions (SSNO-, SNO-, NO2-, S42-, and HS-) using the simple reducing electrophile PPh2Cl. In the case of SSNO- reacting with PPh2Cl, a complex mixture of mono and diphosphorus products is formed exclusively in the P(V) oxidation state. We found that the phosphine stoichiometry dictates selectivity for oxidation to P=S/P=O products or transformation to P2 species. Interestingly, only chalcogen atoms are incorporated into the phosphorus products and, instead, nitrogen is released in the form of NO gas. Finally, we demonstrate that more reducing anions (S42- and HS-) also react with PPh2Cl with P=S bond formation as a key reaction driving force.
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