π-Ligand Exchange on Phosphenium Ions:  Reversible Exchange between Free and Coordinated Alkynes in Phosphirenium Salts

π-Ligand Exchange on Phosphenium Ions:  Reversible Exchange between Free and Coordinated Alkynes in Phosphirenium Salts

The rate of reversible alkyne exchange between 1-methyl-1,2,3-triphenylphosphirenium triflate and ethylphenylacetylene, and that of the reverse reaction between 2-ethyl-1-methyl-1,3-diphenylphosphirenium triflate and diphenylacetylene, are independent of alkyne concentration, which suggests a mechan...

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Bibliographic Details
Published in:Organometallics Vol. 23; no. 2; pp. 299 - 302
Main Authors: Brasch, Nicola E, Hamilton, Ian G, Krenske, Elizabeth H, Wild, S. Bruce
Format: Journal Article
Language:English
Published: American Chemical Society 19-01-2004
Online Access:Get full text
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Summary:The rate of reversible alkyne exchange between 1-methyl-1,2,3-triphenylphosphirenium triflate and ethylphenylacetylene, and that of the reverse reaction between 2-ethyl-1-methyl-1,3-diphenylphosphirenium triflate and diphenylacetylene, are independent of alkyne concentration, which suggests a mechanism that involves rate-determining elimination of alkyne from the phosphirenium triflate to give a transient phosphenium triflate. The mechanism is supported by the observation of crossover products upon mixing phosphirenium triflates containing different substituents.
Bibliography:istex:3A8963ABF470EB51290B4ADC765BAED02B9BD076
ark:/67375/TPS-048ZQ1RG-V
ISSN:0276-7333
1520-6041
DOI:10.1021/om030607z