Metalate-Mediated Functionalization of P4 by Trapping Anionic [Cp*Fe(CO)21-P4)] with Lewis Acids

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

Research output: Contribution to JournalArticleAcademicpeer-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)21-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)21-P4H), allowing controllable stepwise metalate-mediated functionalization of P4.

Original languageEnglish
Pages (from-to)350-353
Number of pages4
JournalChemistryOpen
Volume6
Issue number3
DOIs
Publication statusPublished - 1 Jun 2017

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Lewis Acids
Carbon Monoxide
Transition metals
Anions
Phosphorus
Metals

Keywords

  • anions
  • iron
  • Lewis acids
  • P functionalization
  • white phosphorus

Cite this

Borger, Jaap E. ; Jongkind, Maarten K. ; Ehlers, Andreas W. ; Lutz, Martin ; Slootweg, J. Chris ; Lammertsma, Koop. / Metalate-Mediated Functionalization of P4 by Trapping Anionic [Cp*Fe(CO)21-P4)] with Lewis Acids. In: ChemistryOpen. 2017 ; Vol. 6, No. 3. pp. 350-353.
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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.",
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Metalate-Mediated Functionalization of P4 by Trapping Anionic [Cp*Fe(CO)21-P4)] with Lewis Acids. / Borger, Jaap E.; Jongkind, Maarten K.; Ehlers, Andreas W.; Lutz, Martin; Slootweg, J. Chris; Lammertsma, Koop.

In: ChemistryOpen, Vol. 6, No. 3, 01.06.2017, p. 350-353.

Research output: Contribution to JournalArticleAcademicpeer-review

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AU - Lammertsma, Koop

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