Synthesis and Characterization of Terminal [Re(XCO)(CO)2(triphos)] (X=N, P): Isocyanate versus Phosphaethynolate Complexes

Authors

  • Dr. Simone Alidori,

    1. Department of Chemistry and Applied Biology, ETH Zürich, 8093 Zürich (Switzerland), Fax: (+41) 44-633-10-32
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  • Dominikus Heift,

    1. Department of Chemistry and Applied Biology, ETH Zürich, 8093 Zürich (Switzerland), Fax: (+41) 44-633-10-32
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  • Dr. Gustavo Santiso-Quinones,

    1. Department of Chemistry and Applied Biology, ETH Zürich, 8093 Zürich (Switzerland), Fax: (+41) 44-633-10-32
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  • Dr. Zoltán Benkő,

    1. Department of Chemistry and Applied Biology, ETH Zürich, 8093 Zürich (Switzerland), Fax: (+41) 44-633-10-32
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  • Prof. Dr. Hansjörg Grützmacher,

    Corresponding author
    1. Department of Chemistry and Applied Biology, ETH Zürich, 8093 Zürich (Switzerland), Fax: (+41) 44-633-10-32
    • Department of Chemistry and Applied Biology, ETH Zürich, 8093 Zürich (Switzerland), Fax: (+41) 44-633-10-32
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  • Dr. Maria Caporali,

    1. Istituto di Chimica dei Composti Organometallici, Consiglio Nazionale delle Ricerche (ICCOM-CNR), Via Madonna del Piano 10, 50019 Sesto Fiorentino, Firenze (Italy), Fax: (+39) 055-5225-203
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  • Dr. Luca Gonsalvi,

    1. Istituto di Chimica dei Composti Organometallici, Consiglio Nazionale delle Ricerche (ICCOM-CNR), Via Madonna del Piano 10, 50019 Sesto Fiorentino, Firenze (Italy), Fax: (+39) 055-5225-203
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  • Dr. Andrea Rossin,

    1. Istituto di Chimica dei Composti Organometallici, Consiglio Nazionale delle Ricerche (ICCOM-CNR), Via Madonna del Piano 10, 50019 Sesto Fiorentino, Firenze (Italy), Fax: (+39) 055-5225-203
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  • Dr. Maurizio Peruzzini

    Corresponding author
    1. Istituto di Chimica dei Composti Organometallici, Consiglio Nazionale delle Ricerche (ICCOM-CNR), Via Madonna del Piano 10, 50019 Sesto Fiorentino, Firenze (Italy), Fax: (+39) 055-5225-203
    • Istituto di Chimica dei Composti Organometallici, Consiglio Nazionale delle Ricerche (ICCOM-CNR), Via Madonna del Piano 10, 50019 Sesto Fiorentino, Firenze (Italy), Fax: (+39) 055-5225-203
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Abstract

The terminal rhenium(I) phosphaethynolate complex [Re(PCO)(CO)2(triphos)] has been prepared in a salt metathesis reaction from Na(OCP) and [Re(OTf)(CO)2(triphos)]. The analogous isocyanato complex [Re(NCO)(CO)2(triphos)] has been likewise prepared for comparison. The structure of both complexes was elucidated by X-ray diffraction studies. While the isocyanato complex is linear, the phosphaethynolate complex is strongly bent around the pnictogen center. Computations including natural bond orbital (NBO) theory, natural resonance theory (NRT), and natural population analysis (NPA) indicate that the isocyanato complex can be viewed as a classic Werner-type complex, that is, with an electrostatic interaction between the ReI and the NCO group. The phosphaethynolate complex [Re(P[DOUBLE BOND]C[DOUBLE BOND]O)(CO)2(triphos)] is best described as a metallaphosphaketene with a ReI–phosphorus bond of highly covalent character.

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