Highly Strained Heterometallacycles of Group 4 Metallocenes with Bis(diphenylphosphino)amide Ligands

Authors

  • Martin Haehnel,

    1. Leibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29A, 18059 Rostock (Germany), Fax: (+49) 381-1281-51176, Fax: (+49) 381-1281-51104
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  • Sven Hansen,

    1. Leibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29A, 18059 Rostock (Germany), Fax: (+49) 381-1281-51176, Fax: (+49) 381-1281-51104
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  • Dr. Anke Spannenberg,

    1. Leibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29A, 18059 Rostock (Germany), Fax: (+49) 381-1281-51176, Fax: (+49) 381-1281-51104
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  • Dr. Perdita Arndt,

    1. Leibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29A, 18059 Rostock (Germany), Fax: (+49) 381-1281-51176, Fax: (+49) 381-1281-51104
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  • Dr. Torsten Beweries,

    Corresponding author
    1. Leibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29A, 18059 Rostock (Germany), Fax: (+49) 381-1281-51176, Fax: (+49) 381-1281-51104
    • Leibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29A, 18059 Rostock (Germany), Fax: (+49) 381-1281-51176, Fax: (+49) 381-1281-51104
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  • Prof. Dr. Uwe Rosenthal

    Corresponding author
    1. Leibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29A, 18059 Rostock (Germany), Fax: (+49) 381-1281-51176, Fax: (+49) 381-1281-51104
    • Leibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29A, 18059 Rostock (Germany), Fax: (+49) 381-1281-51176, Fax: (+49) 381-1281-51104
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Abstract

A study regarding coordination chemistry of the bis(diphenylphosphino)amide ligand Ph2P-N-PPh2 at Group 4 metallocenes is presented herein. Coordination of N,N-bis(diphenylphosphino)amine (1) to [(Cp2TiCl)2] (Cp=η5-cyclopentadienyl) generated [Cp2Ti(Cl)P(Ph2)N(H)PPh2] (2). The heterometallacyclic complex [Cp2Ti(κ2-P,P-Ph2P-N-PPh2)] (3 Ti) can be prepared by reaction of 2 with n-butyllithium as well as from the reaction of the known titanocene–alkyne complex [Cp2Ti(η2-Me3SiC2SiMe3)] with the amine 1. Reactions of the lithium amide [(thf)3Li{N(PPh2)2}] with [Cp2MCl2] (M=Zr, Hf) yielded the corresponding zirconocene and hafnocene complexes [Cp2M(Cl){κ2-N,P-N(PPh2)2}] (4 Zr and 4 Hf). Reduction of 4 Zr with magnesium gave the highly strained heterometallacycle [Cp2Zr(κ2-P,P-Ph2P-N-PPh2)] (3 Zr). Complexes 2, 3 Ti, 4 Hf, and 3 Zr were characterized by X-ray crystallography. The structures and bondings of all complexes were investigated by DFT calculations.

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