Formation of Iron−Fluorophosphorane Complexes (η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)(CO)LFe{P(OPh)<i><sub>n</sub></i>F<sub>4</sub><sub>-</sub><i><sub>n</sub></i>} (L = CO, P(OPh)<sub>3</sub>; <i>n</i> = 0, 1) and (η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)(CO)<sub>2</sub>Fe{P(OC<sub>6</sub>H<sub>4</sub>NMe)F<sub>2</sub>}. Nucleophilic Attack of F<sup>-</sup> toward a Trivalent Phosphorus Atom Coordinated to a Transition Metal

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  • Kazuyuki Kubo
    Department of Chemistry, Graduate School of Science, Hiroshima University, Higashi-Hiroshima 739-8526, Japan
  • Kumiko Bansho
    Department of Chemistry, Graduate School of Science, Hiroshima University, Higashi-Hiroshima 739-8526, Japan
  • Hiroshi Nakazawa
    Department of Chemistry, Graduate School of Science, Hiroshima University, Higashi-Hiroshima 739-8526, Japan
  • Katsuhiko Miyoshi
    Department of Chemistry, Graduate School of Science, Hiroshima University, Higashi-Hiroshima 739-8526, Japan

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Description

The reaction of a phosphite complex, [Cp(CO)2Fe{P(OPh)3}]PF6, with Et4NF in CH2Cl2 at room temperature yielded a mixture of metallafluorophosphoranes, Cp(CO)2Fe(PF4) (1) and Cp(CO)2Fe{P(OPh)F3} (2). Similar phosphite complexes [Cp(CO)Fe{P(OPh)3}2]PF6 and also reacted with F- to form Cp(CO){P(OPh)3}Fe(PF4) (3) and (4), respectively. The 31P and 19F NMR studies of these metallafluorophosphoranes revealed that pseudorotation around the hypervalent phosphorus center takes place readily in 1 and 3, whereas it marginally occurs at room temperature in 4, but not in 2 even at elevated temperature. The difference in the energy barrier of the rotation process was interpreted in terms of the apicophilicity of the substituents on the phosphorane phosphorus.

Journal

  • Organometallics

    Organometallics 18 (21), 4311-4316, 1999-09-18

    American Chemical Society (ACS)

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