Selective [3+1] Fragmentations of P4by “P” Transfer from a Lewis Acid Stabilized [RP4]−Butterfly Anion

Jaap E. Borger; Andreas W. Ehlers; Martin Lutz; J. Chris Slootweg; Koop Lammertsma

doi:10.1002/anie.201607234

Selective [3+1] Fragmentations of P₄by “P” Transfer from a Lewis Acid Stabilized [RP₄]⁻Butterfly Anion

Jaap E. Borger, Andreas W. Ehlers, Martin Lutz, J. Chris Slootweg, Koop Lammertsma^*

^*Corresponding author for this work

Research output: Contribution to Journal › Article › Academic › peer-review

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Abstract

Two [3+1] fragmentations of the Lewis acid stabilized bicyclo[1.1.0]tetraphosphabutanide Li[Mes*P₄⋅ BPh₃] (Mes*=2,4,6-tBu₃C₆H₂) are reported. The reactions proceed by extrusion of a P₁fragment, induced by either an imidazolium salt or phenylisocyanate, with release of the transient triphosphirene Mes*P₃, which was isolated as a dimer and trapped by 1,3-cyclohexadiene as a Diels–Alder adduct. DFT quantum chemical computations were used to delineate the reaction mechanisms. These unprecedented pathways grant access to both P₁- and P₃-containing organophosphorus compounds in two simple steps from white phosphorus.

Original language	English
Pages (from-to)	285-290
Number of pages	6
Journal	Angewandte Chemie. International Edition
Volume	56
Issue number	1
Early online date	30 Nov 2016
DOIs	https://doi.org/10.1002/anie.201607234
Publication status	Published - 2 Jan 2017

Keywords

anions
fragmentation
Lewis acids
organophosphorus compounds
phosphorus

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1002/anie.201607234

Borger - Selective 3 1 Fragmentations of P4 by P Transfer from a Lewis Acid Stabilized RP4Final published version, 1.1 MBLicence: Article 25fa Dutch Copyright Act

https://www.infona.pl/resource/bwmeta1.element.wiley-anie-v-56-i-1-anie201607234

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title = "Selective [3+1] Fragmentations of P4by “P” Transfer from a Lewis Acid Stabilized [RP4]−Butterfly Anion",

abstract = "Two [3+1] fragmentations of the Lewis acid stabilized bicyclo[1.1.0]tetraphosphabutanide Li[Mes*P4⋅ BPh3] (Mes*=2,4,6-tBu3C6H2) are reported. The reactions proceed by extrusion of a P1fragment, induced by either an imidazolium salt or phenylisocyanate, with release of the transient triphosphirene Mes*P3, which was isolated as a dimer and trapped by 1,3-cyclohexadiene as a Diels–Alder adduct. DFT quantum chemical computations were used to delineate the reaction mechanisms. These unprecedented pathways grant access to both P1- and P3-containing organophosphorus compounds in two simple steps from white phosphorus.",

keywords = "anions, fragmentation, Lewis acids, organophosphorus compounds, phosphorus",

author = "Borger, {Jaap E.} and Ehlers, {Andreas W.} and Martin Lutz and Slootweg, {J. Chris} and Koop Lammertsma",

year = "2017",

month = jan,

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doi = "10.1002/anie.201607234",

language = "English",

volume = "56",

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T1 - Selective [3+1] Fragmentations of P4by “P” Transfer from a Lewis Acid Stabilized [RP4]−Butterfly Anion

AU - Borger, Jaap E.

AU - Ehlers, Andreas W.

AU - Lutz, Martin

AU - Slootweg, J. Chris

AU - Lammertsma, Koop

PY - 2017/1/2

Y1 - 2017/1/2

N2 - Two [3+1] fragmentations of the Lewis acid stabilized bicyclo[1.1.0]tetraphosphabutanide Li[Mes*P4⋅ BPh3] (Mes*=2,4,6-tBu3C6H2) are reported. The reactions proceed by extrusion of a P1fragment, induced by either an imidazolium salt or phenylisocyanate, with release of the transient triphosphirene Mes*P3, which was isolated as a dimer and trapped by 1,3-cyclohexadiene as a Diels–Alder adduct. DFT quantum chemical computations were used to delineate the reaction mechanisms. These unprecedented pathways grant access to both P1- and P3-containing organophosphorus compounds in two simple steps from white phosphorus.

AB - Two [3+1] fragmentations of the Lewis acid stabilized bicyclo[1.1.0]tetraphosphabutanide Li[Mes*P4⋅ BPh3] (Mes*=2,4,6-tBu3C6H2) are reported. The reactions proceed by extrusion of a P1fragment, induced by either an imidazolium salt or phenylisocyanate, with release of the transient triphosphirene Mes*P3, which was isolated as a dimer and trapped by 1,3-cyclohexadiene as a Diels–Alder adduct. DFT quantum chemical computations were used to delineate the reaction mechanisms. These unprecedented pathways grant access to both P1- and P3-containing organophosphorus compounds in two simple steps from white phosphorus.

KW - anions

KW - fragmentation

KW - Lewis acids

KW - organophosphorus compounds

KW - phosphorus

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JO - Angewandte Chemie. International Edition

JF - Angewandte Chemie. International Edition

IS - 1

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Selective [3+1] Fragmentations of P₄by “P” Transfer from a Lewis Acid Stabilized [RP₄]⁻Butterfly Anion

Abstract

Keywords

UN SDGs

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CCDC 1491989: Experimental Crystal Structure Determination

CCDC 1491990: Experimental Crystal Structure Determination

CCDC 1491988: Experimental Crystal Structure Determination

Cite this

Selective [3+1] Fragmentations of P4by “P” Transfer from a Lewis Acid Stabilized [RP4]−Butterfly Anion

Abstract

Keywords

UN SDGs

Access to Document

Persistent URL (handle)

Other files and links

Fingerprint

Datasets

CCDC 1491989: Experimental Crystal Structure Determination

CCDC 1491990: Experimental Crystal Structure Determination

CCDC 1491988: Experimental Crystal Structure Determination

Cite this

Selective [3+1] Fragmentations of P₄by “P” Transfer from a Lewis Acid Stabilized [RP₄]⁻Butterfly Anion