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Transition Metal Complexes of N-Heterocyclic Germylenes

  1. Farman Ullah1,
  2. Olaf Kühl1,
  3. Gabor Bajor2,
  4. Tamas Veszprémi2,
  5. Peter G. Jones3,
  6. Joachim Heinicke1

Article first published online: 29 OCT 2008

DOI: 10.1002/ejic.200800849

Issue

European Journal of Inorganic Chemistry

European Journal of Inorganic Chemistry

Volume 2009, Issue 2, pages 221–229, January 2009

Additional Information

How to Cite

Ullah, F., Kühl, O., Bajor, G., Veszprémi, T., Jones, P. G. and Heinicke, J. (2009), Transition Metal Complexes of N-Heterocyclic Germylenes. Eur. J. Inorg. Chem., 2009: 221–229. doi: 10.1002/ejic.200800849

Author Information

  1. 1

    Institut für Biochemie – Anorganische Chemie, Ernst-Moritz-Arndt-Universität Greifswald, Felix-Hausdorff-Str. 4, 17487 Greifswald, Germany, Fax: +49-3834-864377

  2. 2

    Department of Inorganic Chemistry, Technical University of Budapest, 1521 Budapest, Hungary

  3. 3

    Institut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Hagenring 30, 38106 Braunschweig, Germany

Publication History

  1. Issue published online: 29 DEC 2008
  2. Article first published online: 29 OCT 2008
  3. Manuscript Received: 24 AUG 2008

Funded by

  • OTKA. Grant Number: T048796

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Keywords:

  • Germanium;
  • Molybdenum;
  • Nickel;
  • Carbenoids;
  • Quantum chemical calculations

Abstract

The five-membered N-heterocyclic germylenes (NHGe) 1a–3a, with or without benzo or naphtho anellation, react with [Mo(CO)3(cht)] (cht = 1,3,5-cycloheptatriene) to form thefac-[(NHGe)3Mo(CO)3] complexes 1b–3b. Similarly, [Ni(bnNHGe)4] was obtained from the benzo-anellated germylene (bnNHGe) and Ni(1,5-cod)2; attempts to synthesize less electron-rich complexes with mono- or divalent transition metals failed. The CO valence vibrations in the IR spectra of 1b–3b, together with their short GeII–Mo bonds (as determined by X-ray crystallography), hint at the weak donor and good π-acceptor properties of the ligands. Quantum chemical studies on the benzo-anellated germylene, which are supported by the good correlation between calculated and experimental (PES) orbital ionization potentials, confirm this proposal in terms of the low energy of the Ge lone electron pair and two higher π-MOs. The slight folding about the C–C bridging and N···N axes observed for the benzo-anellated (NHGe)molybdenum and -nickel complexes by X-ray structure analyses, may be due to packing effects. Quantum chemical calculations on slightly bent (for dineopentyl substitution in the gas phase) and planar bnNHGe complexes show that the energy differences between the two are very small.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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