Metalate-Mediated Functionalization of P4 by Trapping Anionic [Cp*Fe(CO)2(η1-P4)]− with Lewis Acids

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

doi:10.1002/open.201700027

Metalate-Mediated Functionalization of P₄ by Trapping Anionic [Cp*Fe(CO)₂(η¹-P₄)]⁻ with Lewis Acids

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

^*Corresponding author for this work

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

Abstract

The development of selective functionalization strategies of white phosphorus (P₄) is important to avoid the current chlorinated intermediates. The use of transition metals (TMs) could lead to catalytic procedures, but these are severely hampered by the high reactivity and unpredictable nature of the tetrahedron. Herein, we report selective first steps by reacting P₄ with a metal anion [Cp*Fe(CO)₂]⁻ (Cp*=C₅(CH₃)₅), which, in the presence of bulky Lewis acids (LA; B(C₆F₅)₃ or BPh₃), leads to unique TM-substituted LA-stabilized bicyclo[1.1.0]tetraphosphabutanide anions [Cp*Fe(CO)₂(η¹-P₄⋅LA)]⁻. Their P-nucleophilic site can be subsequently protonated to afford the transient LA-free neutral butterflies exo,endo- and exo,exo-Cp*Fe- (CO)₂(η¹-P₄H), allowing controllable stepwise metalate-mediated functionalization of P₄.

Original language	English
Pages (from-to)	350-353
Number of pages	4
Journal	ChemistryOpen
Volume	6
Issue number	3
DOIs	https://doi.org/10.1002/open.201700027
Publication status	Published - 1 Jun 2017

Funding

This work was supported by the Council for Chemical Sciences of the Netherlands Organization for Scientific Research (NWO/CW).

Funders	Funder number
Nederlandse Organisatie voor Wetenschappelijk Onderzoek

Keywords

anions
iron
Lewis acids
P functionalization
white phosphorus

UN SDGs

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

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10.1002/open.201700027

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@article{60f8f63229b14d8195a16e872c26660f,

title = "Metalate-Mediated Functionalization of P4 by Trapping Anionic [Cp*Fe(CO)2(η1-P4)]− with Lewis Acids",

abstract = "The development of selective functionalization strategies of white phosphorus (P4) is important to avoid the current chlorinated intermediates. The use of transition metals (TMs) could lead to catalytic procedures, but these are severely hampered by the high reactivity and unpredictable nature of the tetrahedron. Herein, we report selective first steps by reacting P4 with a metal anion [Cp*Fe(CO)2]− (Cp*=C5(CH3)5), which, in the presence of bulky Lewis acids (LA; B(C6F5)3 or BPh3), leads to unique TM-substituted LA-stabilized bicyclo[1.1.0]tetraphosphabutanide anions [Cp*Fe(CO)2(η1-P4⋅LA)]−. Their P-nucleophilic site can be subsequently protonated to afford the transient LA-free neutral butterflies exo,endo- and exo,exo-Cp*Fe- (CO)2(η1-P4H), allowing controllable stepwise metalate-mediated functionalization of P4.",

keywords = "anions, iron, Lewis acids, P functionalization, white phosphorus",

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

year = "2017",

month = jun,

day = "1",

doi = "10.1002/open.201700027",

language = "English",

volume = "6",

pages = "350--353",

journal = "ChemistryOpen",

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T1 - Metalate-Mediated Functionalization of P4 by Trapping Anionic [Cp*Fe(CO)2(η1-P4)]− with Lewis Acids

AU - Borger, Jaap E.

AU - Jongkind, Maarten K.

AU - Ehlers, Andreas W.

AU - Lutz, Martin

AU - Slootweg, J. Chris

AU - Lammertsma, Koop

PY - 2017/6/1

Y1 - 2017/6/1

N2 - The development of selective functionalization strategies of white phosphorus (P4) is important to avoid the current chlorinated intermediates. The use of transition metals (TMs) could lead to catalytic procedures, but these are severely hampered by the high reactivity and unpredictable nature of the tetrahedron. Herein, we report selective first steps by reacting P4 with a metal anion [Cp*Fe(CO)2]− (Cp*=C5(CH3)5), which, in the presence of bulky Lewis acids (LA; B(C6F5)3 or BPh3), leads to unique TM-substituted LA-stabilized bicyclo[1.1.0]tetraphosphabutanide anions [Cp*Fe(CO)2(η1-P4⋅LA)]−. Their P-nucleophilic site can be subsequently protonated to afford the transient LA-free neutral butterflies exo,endo- and exo,exo-Cp*Fe- (CO)2(η1-P4H), allowing controllable stepwise metalate-mediated functionalization of P4.

AB - The development of selective functionalization strategies of white phosphorus (P4) is important to avoid the current chlorinated intermediates. The use of transition metals (TMs) could lead to catalytic procedures, but these are severely hampered by the high reactivity and unpredictable nature of the tetrahedron. Herein, we report selective first steps by reacting P4 with a metal anion [Cp*Fe(CO)2]− (Cp*=C5(CH3)5), which, in the presence of bulky Lewis acids (LA; B(C6F5)3 or BPh3), leads to unique TM-substituted LA-stabilized bicyclo[1.1.0]tetraphosphabutanide anions [Cp*Fe(CO)2(η1-P4⋅LA)]−. Their P-nucleophilic site can be subsequently protonated to afford the transient LA-free neutral butterflies exo,endo- and exo,exo-Cp*Fe- (CO)2(η1-P4H), allowing controllable stepwise metalate-mediated functionalization of P4.

KW - anions

KW - iron

KW - Lewis acids

KW - P functionalization

KW - white phosphorus

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Metalate-Mediated Functionalization of P₄ by Trapping Anionic [Cp*Fe(CO)₂(η¹-P₄)]⁻ with Lewis Acids

Abstract

Funding

Keywords

UN SDGs

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CCDC 1509067: Experimental Crystal Structure Determination

Cite this

Metalate-Mediated Functionalization of P4 by Trapping Anionic [Cp*Fe(CO)2(η1-P4)]− with Lewis Acids

Abstract

Funding

Keywords

UN SDGs

Access to Document

Persistent URL (handle)

Other files and links

Fingerprint

Datasets

CCDC 1509067: Experimental Crystal Structure Determination

Cite this

Metalate-Mediated Functionalization of P₄ by Trapping Anionic [Cp*Fe(CO)₂(η¹-P₄)]⁻ with Lewis Acids