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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
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- Kumiko Bansho
- Department of Chemistry, Graduate School of Science, Hiroshima University, Higashi-Hiroshima 739-8526, Japan
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- Hiroshi Nakazawa
- Department of Chemistry, Graduate School of Science, Hiroshima University, Higashi-Hiroshima 739-8526, Japan
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- 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
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- Organometallics
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Organometallics 18 (21), 4311-4316, 1999-09-18
American Chemical Society (ACS)
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Details 詳細情報について
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- CRID
- 1363670321337078784
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- ISSN
- 15206041
- 02767333
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- Data Source
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- Crossref
- OpenAIRE