Synthesis and ligand properties of 1-phosphaethenyl-2-phosphanylferrocenes

Ryo Takita, Yuko Takada, Rader S. Jensen, Masaaki Okazaki, Fumiyuki Ozawa

    Research output: Contribution to journalArticle

    17 Citations (Scopus)

    Abstract

    (S)-1-Phosphaemenyl-2-diarylphosphanylferrocenes with planar chirality (Fc(CH=PMes*)PAr2: PAr2 = PPh2 (3a), P(1-naphmyl)Ph (3b)) are prepared in high yields from optically active 2-phosphanylferrocenecarboxaldehydes by the phospha-Peterson reactions with Mes*P(Li)SiMe3 in THF. The stereo-chemistry of 3b is determined by X-ray diffraction analysis. Compounds 3a and 3b readily react with [PtMe2(μ-SMe2)]2 in Et2O to afford dimethyl complexes with bidentate coordination of these ligands (PtMe2(L): L = 3a (4a), 3b (4b)). The X-ray structure of 4b reveals almost identical trans-influence of the phosphaethenyl and phosphanyl groups, snowing comparable cr-donating abilities of those components. Treatment of 3a and 3b with [Pd(η3-allyl)(μ-Cl)]2 in CH 2Cl2 in the presence of AgOTf forms the corresponding π-allyl complexes [Pd(η3-allyl)(L)]OTf (L = 3a (5a), 3b (5b)), respectively, which are mixtures of diastereomers with endo- and exo-oriented π-allyl ligands. Complex 5a catalyzes hydroamination of 1,3-cyclohexadiene with aniline in toluene in the presence of 5 A molecular sieves at room temperature, giving N-cyclohexen-3-ylaniline in 84% yield.

    Original languageEnglish
    Pages (from-to)6279-6285
    Number of pages7
    JournalOrganometallics
    Volume27
    Issue number23
    DOIs
    Publication statusPublished - 2008 Dec 8

    Fingerprint

    methylidyne
    Ligands
    ligands
    Stereochemistry
    Chirality
    Molecular sieves
    stereochemistry
    Toluene
    absorbents
    synthesis
    aniline
    chirality
    X ray diffraction analysis
    toluene
    x rays
    X rays
    room temperature
    diffraction
    Temperature
    1,3-cyclohexadiene

    ASJC Scopus subject areas

    • Organic Chemistry
    • Physical and Theoretical Chemistry
    • Inorganic Chemistry

    Cite this

    Takita, R., Takada, Y., Jensen, R. S., Okazaki, M., & Ozawa, F. (2008). Synthesis and ligand properties of 1-phosphaethenyl-2-phosphanylferrocenes. Organometallics, 27(23), 6279-6285. https://doi.org/10.1021/om8008316

    Synthesis and ligand properties of 1-phosphaethenyl-2-phosphanylferrocenes. / Takita, Ryo; Takada, Yuko; Jensen, Rader S.; Okazaki, Masaaki; Ozawa, Fumiyuki.

    In: Organometallics, Vol. 27, No. 23, 08.12.2008, p. 6279-6285.

    Research output: Contribution to journalArticle

    Takita, R, Takada, Y, Jensen, RS, Okazaki, M & Ozawa, F 2008, 'Synthesis and ligand properties of 1-phosphaethenyl-2-phosphanylferrocenes', Organometallics, vol. 27, no. 23, pp. 6279-6285. https://doi.org/10.1021/om8008316
    Takita R, Takada Y, Jensen RS, Okazaki M, Ozawa F. Synthesis and ligand properties of 1-phosphaethenyl-2-phosphanylferrocenes. Organometallics. 2008 Dec 8;27(23):6279-6285. https://doi.org/10.1021/om8008316
    Takita, Ryo ; Takada, Yuko ; Jensen, Rader S. ; Okazaki, Masaaki ; Ozawa, Fumiyuki. / Synthesis and ligand properties of 1-phosphaethenyl-2-phosphanylferrocenes. In: Organometallics. 2008 ; Vol. 27, No. 23. pp. 6279-6285.
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    AB - (S)-1-Phosphaemenyl-2-diarylphosphanylferrocenes with planar chirality (Fc(CH=PMes*)PAr2: PAr2 = PPh2 (3a), P(1-naphmyl)Ph (3b)) are prepared in high yields from optically active 2-phosphanylferrocenecarboxaldehydes by the phospha-Peterson reactions with Mes*P(Li)SiMe3 in THF. The stereo-chemistry of 3b is determined by X-ray diffraction analysis. Compounds 3a and 3b readily react with [PtMe2(μ-SMe2)]2 in Et2O to afford dimethyl complexes with bidentate coordination of these ligands (PtMe2(L): L = 3a (4a), 3b (4b)). The X-ray structure of 4b reveals almost identical trans-influence of the phosphaethenyl and phosphanyl groups, snowing comparable cr-donating abilities of those components. Treatment of 3a and 3b with [Pd(η3-allyl)(μ-Cl)]2 in CH 2Cl2 in the presence of AgOTf forms the corresponding π-allyl complexes [Pd(η3-allyl)(L)]OTf (L = 3a (5a), 3b (5b)), respectively, which are mixtures of diastereomers with endo- and exo-oriented π-allyl ligands. Complex 5a catalyzes hydroamination of 1,3-cyclohexadiene with aniline in toluene in the presence of 5 A molecular sieves at room temperature, giving N-cyclohexen-3-ylaniline in 84% yield.

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