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An Unusal Case of Facile Non-Degenerate P[BOND]C Bond Making and Breaking

Authors

  • Dr. Vitaly Nesterov,

    1. Institut für Anorganische Chemie der Rheinischen Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Str. 1, 53121 Bonn (Germany), Fax: (+49) 228-739616
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  • Aysel Özbolat-Schön,

    1. Institut für Anorganische Chemie der Rheinischen Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Str. 1, 53121 Bonn (Germany), Fax: (+49) 228-739616
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  • Dr. Gregor Schnakenburg,

    1. Institut für Anorganische Chemie der Rheinischen Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Str. 1, 53121 Bonn (Germany), Fax: (+49) 228-739616
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  • Dr. Lili Shi,

    1. Max Planck Institut für Bioanorganische Chemie, Stiftstrasse 34-36, 45470 Mülheim an der Ruhr (Germany), Fax: (+49) 208-306-3951
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  • Asli Cangönül,

    1. Max Planck Institut für Bioanorganische Chemie, Stiftstrasse 34-36, 45470 Mülheim an der Ruhr (Germany), Fax: (+49) 208-306-3951
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  • Dr. Maurice van Gastel,

    1. Max Planck Institut für Bioanorganische Chemie, Stiftstrasse 34-36, 45470 Mülheim an der Ruhr (Germany), Fax: (+49) 208-306-3951
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  • Prof. Dr. Frank Neese,

    Corresponding author
    1. Max Planck Institut für Bioanorganische Chemie, Stiftstrasse 34-36, 45470 Mülheim an der Ruhr (Germany), Fax: (+49) 208-306-3951
    • Frank Neese, Max Planck Institut für Bioanorganische Chemie, Stiftstrasse 34-36, 45470 Mülheim an der Ruhr (Germany), Fax: (+49) 208-306-3951

      Rainer Streubel, Institut für Anorganische Chemie der Rheinischen Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Str. 1, 53121 Bonn (Germany), Fax: (+49) 228-739616

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  • Prof. Dr. Rainer Streubel

    Corresponding author
    1. Institut für Anorganische Chemie der Rheinischen Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Str. 1, 53121 Bonn (Germany), Fax: (+49) 228-739616
    • Frank Neese, Max Planck Institut für Bioanorganische Chemie, Stiftstrasse 34-36, 45470 Mülheim an der Ruhr (Germany), Fax: (+49) 208-306-3951

      Rainer Streubel, Institut für Anorganische Chemie der Rheinischen Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Str. 1, 53121 Bonn (Germany), Fax: (+49) 228-739616

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Abstract

Oxidation of Li/X phosphinidenoid complex , obtained via selective deprotonation from the P-H precursor , with [Ph3C]BF4 led to the formation of two P-F substituted diorganophosphane complexes 6,; the latter tautomer formed via H-shift from 6. In contrast, oxidation of with [(p-Tol)3C]BF4 led to three major and one minor intermediates at low temperature, which we tentatively assign to two pairs of P-C atropisomers ,a′ and ,c′ and which differ by the relative orientations of their CH(SiMe3)2 and W(CO)5 groups. Conversion of all isomers led finally to complex having a ligand with a long P[BOND]C bond to the central trityl* carbon atom, firmly established by single-crystal X-ray analysis. DFT calculations at the B3LYP/def2-TZVPP//BP86/def2-TZVP level of theory on real molecular entities revealed the structures of the in situ formed combined singlet diradicals (4+5 and 5+9) and the nature of intermediates on the way to the final product, complex . Remarkable is that all isomers of possess relative energies in the narrow energy regime of about 20 kcal mol−1. A preliminary study revealed that complex undergoes selective P[BOND]C bond cleavage at 75 °C in toluene solution.

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