Reactivity of phosphiranes toward nucleophiles: Theoretical and experimental investigations

Michelle L. Coote; Elizabeth H. Krenske; Ilham Maulana; Jörg Steinbach; S. Bruce Wild

doi:10.1002/hc.20405

Reactivity of phosphiranes toward nucleophiles: Theoretical and experimental investigations

Michelle L. Coote^*, Elizabeth H. Krenske, Ilham Maulana, Jörg Steinbach, S. Bruce Wild

^*Corresponding author for this work

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

9 Citations (Scopus)

Abstract

The thermodynamic and kinetic parameters for the reaction of 1-methylphosphirane with dimethylphosphide (PMe₂^-), proceeding via attack at the ring phosphorus atom to give Me₂P- PMe^- plus ethylene, were calculated at the G3(MP2)-RAD(+) level. The rate constant for this mechanism (k= 1.1 × 10^-13 L mol ^-1 s^-1 at 25°C) is seven orders of magnitude greater than that for the previously studied mechanism involving attack at carbon. Experimental investigations with 1-phenylphosphirane gave consistent results: Treatment with LiPMePh yielded no detectable polymer, and quenching with MeI gave the known diphosphine (R*, R*)-(±)/(R*,S*)- MePhP-PMePh.

Original language	English
Pages (from-to)	178-181
Number of pages	4
Journal	Heteroatom Chemistry
Volume	19
Issue number	2
DOIs	https://doi.org/10.1002/hc.20405
Publication status	Published - 2008

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@article{9685ecf614dc4893a2d906631dcbc6cc,

title = "Reactivity of phosphiranes toward nucleophiles: Theoretical and experimental investigations",

abstract = "The thermodynamic and kinetic parameters for the reaction of 1-methylphosphirane with dimethylphosphide (PMe2-), proceeding via attack at the ring phosphorus atom to give Me2P- PMe- plus ethylene, were calculated at the G3(MP2)-RAD(+) level. The rate constant for this mechanism (k= 1.1 × 10-13 L mol -1 s-1 at 25°C) is seven orders of magnitude greater than that for the previously studied mechanism involving attack at carbon. Experimental investigations with 1-phenylphosphirane gave consistent results: Treatment with LiPMePh yielded no detectable polymer, and quenching with MeI gave the known diphosphine (R*, R*)-(±)/(R*,S*)- MePhP-PMePh.",

author = "Coote, \{Michelle L.\} and Krenske, \{Elizabeth H.\} and Ilham Maulana and J{\"o}rg Steinbach and Wild, \{S. Bruce\}",

year = "2008",

doi = "10.1002/hc.20405",

language = "English",

volume = "19",

pages = "178--181",

journal = "Heteroatom Chemistry",

issn = "1042-7163",

publisher = "John Wiley \& Sons Inc.",

number = "2",

}

TY - JOUR

T1 - Reactivity of phosphiranes toward nucleophiles

T2 - Theoretical and experimental investigations

AU - Coote, Michelle L.

AU - Krenske, Elizabeth H.

AU - Maulana, Ilham

AU - Steinbach, Jörg

AU - Wild, S. Bruce

PY - 2008

Y1 - 2008

N2 - The thermodynamic and kinetic parameters for the reaction of 1-methylphosphirane with dimethylphosphide (PMe2-), proceeding via attack at the ring phosphorus atom to give Me2P- PMe- plus ethylene, were calculated at the G3(MP2)-RAD(+) level. The rate constant for this mechanism (k= 1.1 × 10-13 L mol -1 s-1 at 25°C) is seven orders of magnitude greater than that for the previously studied mechanism involving attack at carbon. Experimental investigations with 1-phenylphosphirane gave consistent results: Treatment with LiPMePh yielded no detectable polymer, and quenching with MeI gave the known diphosphine (R*, R*)-(±)/(R*,S*)- MePhP-PMePh.

AB - The thermodynamic and kinetic parameters for the reaction of 1-methylphosphirane with dimethylphosphide (PMe2-), proceeding via attack at the ring phosphorus atom to give Me2P- PMe- plus ethylene, were calculated at the G3(MP2)-RAD(+) level. The rate constant for this mechanism (k= 1.1 × 10-13 L mol -1 s-1 at 25°C) is seven orders of magnitude greater than that for the previously studied mechanism involving attack at carbon. Experimental investigations with 1-phenylphosphirane gave consistent results: Treatment with LiPMePh yielded no detectable polymer, and quenching with MeI gave the known diphosphine (R*, R*)-(±)/(R*,S*)- MePhP-PMePh.

UR - https://www.scopus.com/pages/publications/40749154881

U2 - 10.1002/hc.20405

DO - 10.1002/hc.20405

M3 - Article

SN - 1042-7163

VL - 19

SP - 178

EP - 181

JO - Heteroatom Chemistry

JF - Heteroatom Chemistry

IS - 2

ER -

Reactivity of phosphiranes toward nucleophiles: Theoretical and experimental investigations

Abstract

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