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

Chemical Sciences

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

11 Citations (Scopus)

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

Keywords

Lewis acids
P functionalization
anions
iron
white phosphorus

ASJC Scopus subject areas

General Chemistry

Access to Document

10.1002/open.201700027

Cite this

@article{544ef0c85a2e45699219b33c5478b7dd,

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

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

note = "Publisher Copyright: {\textcopyright} 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.",

year = "2017",

month = jun,

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doi = "10.1002/open.201700027",

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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 - Lewis acids

KW - P functionalization

KW - anions

KW - iron

KW - white phosphorus

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