The Complex Amide K2[Zr(NH2)6]

Authors

  • Dr. Florian Kraus,

    Corresponding author
    1. AG Fluorchemie, Department Chemie, Technische Universität München, Lichtenbergstrasse 4, 85747 Garching, Germany
    • AG Fluorchemie, Department Chemie, Technische Universität München, Lichtenbergstrasse 4, 85747 Garching, Germany, Fax: +49-89-289-13762
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  • Sebastian A. Baer,

    1. AG Fluorchemie, Department Chemie, Technische Universität München, Lichtenbergstrasse 4, 85747 Garching, Germany
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  • Antti J. Karttunen

    1. University of Eastern Finland, Department of Chemistry, P.O. Box 111, 80101 Joensuu, Finland
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  • Dedicated to Professor Hanskarl Müller-Buschbaum on the Occasion of His 80th Birthday

  • Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/zaac.201100083 or from the author.

Abstract

We present the low-temperature synthesis of potassium hexaamido zirconate(IV) from the transition metal tetrafluoride and thealkali metal dissolved in liquid ammonia at –40 °C. Potassium hexaamido zirconate(IV) K2[Zr(NH2)6] is the first ternary amide reported for elements of group 4 of the periodic table It crystallizes with a novel structure type in the trigonal space group Requation imagec with a = 6.5422(2) Å, c = 32.824(2) Å, V = 1216.66(9) Å3, Z = 6 and c/a = 5.017. The structure can be derived from the K2PtCl6 type. The compound contains discrete D3-symmetric [Zr(NH2)6]2– anions which differ significantly from octahedral shape. Quantum chemical calculations show the distortion to arise from a splitting of degenerate d-orbitals on the zirconium atom leading to a significant gain in energy.

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