2,6-Dimethoxyphenylphosphirane oxide and sulfide and their thermolysis to phosphinidene chalcogenides - Kinetic and mechanistic studies

Peter P. Gaspar, Hu Qian, Alicia M. Beatty, D. André D'Avignon, Jeff L.F. Kao, Jesse C. Watt, Nigam P. Rath

Research output: Contribution to journalArticlepeer-review

27 Scopus citations

Abstract

2,6-Dimethoxyphenylphosphirane is readily converted to its oxide and sulfide whose pyrolysis and (perhaps) photolysis lead to the generation of phosphinidene chalcogenides Ar-P=Z (Z=O,S). Trapping experiments were carried out under conditions similar to the kinetic studies of the phosphirane chalcogenide pyrolyses that confirmed the formation of free Ar-P=Z. The trapping experiments were in accord with carbene-like character for Ar-P=Z, and the activation parameters suggest a non-least motion pathway for the addition of Ar-P=Z to olefins. This represents quantitative evidence for the validity of the predictions of frontier-orbital theory for species that undergo reactions with small (or no) enthalpic barriers.

Original languageEnglish (US)
Pages (from-to)105-119
Number of pages15
JournalTetrahedron
Volume56
Issue number1
DOIs
StatePublished - Jan 1 2000
Externally publishedYes

Bibliographical note

Funding Information:
This work has received financial support from National Science Foundation Grant CHE-9632897. NMR instrumentation was made available in part through NIH Shared Instrument Grants RR-02004, RR-05018 and RR-07155. Dr Frank Borkenhagen provided valuable experimental advice.

Copyright:
Copyright 2004 Elsevier Science B.V., Amsterdam. All rights reserved.

Keywords

  • Phosphine oxides
  • Phosphine sulfides
  • Phosphorus heterocycles
  • Strained compounds

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