Evidence for the involvement of pentacoordinate P-intermediates during the UV light-mediated fragmentation of a 2-phosphabicyclo[2.2.2]octene 2-oxide in the presence of O-nucleophiles

Stefan Jankowski, Juliusz Rudzinski, Helga Szelke, G. Keglevich

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

Isotope-exchange experiments with H218O proved at least the partial involvement of a P(V)-species (8) as an intermediate in the UV light-promoted fragmentation of phosphabicyclooctene (1). Selection between the alcohols of equimolar mixtures during the photochemical fragmentation of 1 also suggests a mechanism where an adduct (4) is formed in the rate-determining step affording the phosphorylated product (5) after decomposition. We were able to prove that the transient adduct (4) is formed in a reversible manner.

Original languageEnglish
Pages (from-to)109-113
Number of pages5
JournalJournal of Organometallic Chemistry
Volume595
Issue number1
Publication statusPublished - Jan 31 2000

Fingerprint

Nucleophiles
nucleophiles
Ultraviolet Rays
Isotopes
Ultraviolet radiation
Oxides
adducts
fragmentation
Alcohols
Decomposition
oxides
alcohols
isotopes
Experiments
decomposition
products

Keywords

  • Fragmentation
  • Mechanism
  • Nucleophility
  • Pentacoordinated intermediate
  • Photolysis
  • Reversibility

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

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T1 - Evidence for the involvement of pentacoordinate P-intermediates during the UV light-mediated fragmentation of a 2-phosphabicyclo[2.2.2]octene 2-oxide in the presence of O-nucleophiles

AU - Jankowski, Stefan

AU - Rudzinski, Juliusz

AU - Szelke, Helga

AU - Keglevich, G.

PY - 2000/1/31

Y1 - 2000/1/31

N2 - Isotope-exchange experiments with H218O proved at least the partial involvement of a P(V)-species (8) as an intermediate in the UV light-promoted fragmentation of phosphabicyclooctene (1). Selection between the alcohols of equimolar mixtures during the photochemical fragmentation of 1 also suggests a mechanism where an adduct (4) is formed in the rate-determining step affording the phosphorylated product (5) after decomposition. We were able to prove that the transient adduct (4) is formed in a reversible manner.

AB - Isotope-exchange experiments with H218O proved at least the partial involvement of a P(V)-species (8) as an intermediate in the UV light-promoted fragmentation of phosphabicyclooctene (1). Selection between the alcohols of equimolar mixtures during the photochemical fragmentation of 1 also suggests a mechanism where an adduct (4) is formed in the rate-determining step affording the phosphorylated product (5) after decomposition. We were able to prove that the transient adduct (4) is formed in a reversible manner.

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KW - Mechanism

KW - Nucleophility

KW - Pentacoordinated intermediate

KW - Photolysis

KW - Reversibility

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