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2-Bromophospholide ions: synthesis and theoretical study.

Eliane Deschamps1, François Mathey

  • 1Laboratoire Hétéroéléments et Coordination, UMR CNRS 7653, DCPH, Ecole Polytechnique, 91128 Palaiseau Cedex, France.

Chemistry (Weinheim an Der Bergstrasse, Germany)
|July 23, 2005
PubMed
Summary

The 2-bromophospholide ion is stable due to reduced phosphorus lone pair nucleophilicity. Its synthesis and reaction with iron(II) chloride yielded a dibromodiphosphaferrocene derivative.

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Concise Synthesis of Phospholene and Its P-Stereogenic Derivatives.

The Journal of organic chemistry·2020

Area of Science:

  • Organometallic Chemistry
  • Computational Chemistry
  • Synthetic Chemistry

Background:

  • Phospholide ions are important intermediates in organophosphorus chemistry.
  • Understanding their reactivity, particularly towards self-arylation, is crucial for synthetic applications.
  • Previous studies have not fully elucidated the stability and reactivity of brominated phospholide ions.

Purpose of the Study:

  • To investigate the stability of the 2-bromophospholide ion against self-arylation using computational methods.
  • To synthesize the 2-bromo-3,4-dimethylphospholide ion.
  • To explore the reactivity of this ion with iron(II) chloride for potential diphosphaferrocene formation.

Main Methods:

  • Density Functional Theory (DFT) calculations at the B3 LYP/6-311++G(3df,2p) level.

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  • Synthesis via quantitative base-induced dealkylation of a precursor phosphole.
  • Reaction of the synthesized phospholide ion with iron(II) chloride (FeCl2).

    • Main Results:

    • DFT calculations predicted enhanced stability of the 2-bromophospholide ion due to a lowered in-plane phosphorus lone pair orbital energy (-0.7 eV) and reduced negative charge at phosphorus (-0.369 e).
    • Successful synthesis of 2-bromo-3,4-dimethylphospholide was achieved.
    • Reaction with FeCl2 yielded 2,2'-dibromo-3,3',4,4'-tetramethyl-1,1'-diphosphaferrocene as a mixture of diastereomers in 18% yield, though poorly stable.

    Conclusions:

    • The 2-bromophospholide ion exhibits inherent stability against self-arylation, contrary to potential expectations.
    • The synthetic route provides access to functionalized phospholide ions.
    • The formation of the dibromodiphosphaferrocene derivative demonstrates a viable, albeit low-yielding, pathway to novel organometallic compounds.