Meerwein reaction of phosphonium ions with epoxides and thioepoxides in the gas phase

Eduardo C. Meurer, Hao Chen, Leah S. Riter, R. Graham Cooks, Marcos N. Eberlin

Research output: Contribution to journalArticlepeer-review

14 Scopus citations

Abstract

Phosphonium ions are shown to undergo a gas-phase Meerwein reaction in which epoxides (or thioepoxides) undergo three-to-five-membered ring expansion to yield dioxaphospholanium (or oxathiophospholanium) ion products. When the association reaction is followed by collision-induced dissociation (CID), the oxirane (or thiirane) is eliminated, making this ion molecule reaction/CID sequence a good method of net oxygen-by-sulfur replacement in the phosphonium ions. This replacement results in a characteristic mass shift of 16 units and provides evidence for the cyclic nature of the gas-phase Meerwein product ions, while improving selectivity for phosphonium ion detection. This reaction sequence also constitutes a gas-phase route to convert phosphonium ions into their sulfur analogs. Phosphonium and related ions are important targets since they are commonly and readily formed in mass spectrometric analysis upon dissociative electron ionization of organophosphorous esters. The Meerwein reaction should provide a new and very useful method of recognizing compounds that yield these ions, which includes a number of chemical warfare agents. The Meerwein reaction proceeds by phosphonium ion addition to the sulfur or oxygen center, followed by intramolecular nucleophilic attack with ring expansion to yield the 1,3,2-dioxaphospholanium or 1,3,2-oxathiophospholanium ion. Product ion structures were investigated by CID tandem mass spectrometry (MS 2) experiments and corroborated by DFT/HF calculations.

Original languageEnglish (US)
Pages (from-to)398-405
Number of pages8
JournalJournal of the American Society for Mass Spectrometry
Volume15
Issue number3
DOIs
StatePublished - Mar 2004
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Structural Biology
  • Spectroscopy

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