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

Nicola E. Brasch; Ian G. Hamilton; Elizabeth H. Krenske; S. Bruce Wild

doi:10.1021/om030607z

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

Nicola E. Brasch^*, Ian G. Hamilton, Elizabeth H. Krenske, S. Bruce Wild

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

25 Citations (Scopus)

Abstract

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.

Original language	English
Pages (from-to)	299-302
Number of pages	4
Journal	Organometallics
Volume	23
Issue number	2
DOIs	https://doi.org/10.1021/om030607z
Publication status	Published - 19 Jan 2004

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

abstract = "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.",

author = "Brasch, {Nicola E.} and Hamilton, {Ian G.} and Krenske, {Elizabeth H.} and Wild, {S. Bruce}",

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T2 - Reversible Exchange between Free and Coordinated Alkynes in Phosphirenium Salts

AU - Brasch, Nicola E.

AU - Hamilton, Ian G.

AU - Krenske, Elizabeth H.

AU - Wild, S. Bruce

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Y1 - 2004/1/19

N2 - 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.

AB - 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.

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DO - 10.1021/om030607z

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JO - Organometallics

JF - Organometallics

IS - 2

ER -

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

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