Communication

Remarkable Stability of Metallocenes with Superbulky Ligands: Spontaneous Reduction of SmIII to SmII†

  1. Christian Ruspic1,
  2. John R. Moss Prof. Dr.2,
  3. Markus Schürmann Dr.3,
  4. Sjoerd Harder Prof. Dr.1

Article first published online: 6 FEB 2008

DOI: 10.1002/anie.200705001

Issue

Angewandte Chemie International Edition

Angewandte Chemie International Edition

Volume 47, Issue 11, pages 2121–2126, February 28, 2008

Additional Information

How to Cite

Ruspic, C., Moss, John R., Schürmann, M. and Harder, S. (2008), Remarkable Stability of Metallocenes with Superbulky Ligands: Spontaneous Reduction of SmIII to SmII. Angew. Chem. Int. Ed., 47: 2121–2126. doi: 10.1002/anie.200705001

Author Information

  1. 1

    Anorganische Chemie, Universität Duisburg-Essen, Universitätsstrasse 5, 45117 Essen, Germany, Fax: (+49) 201-183-2621

  2. 2

    Department of Chemistry, University of Cape Town, Rondebosch 7701, Cape Town, South Africa

  3. 3

    Anorganische Chemie, Universität Dortmund, 44221 Dortmund, Germany

  1. †

    S.H. kindly acknowledges the University of Cape Town for an extensive research stay in the autumn of 2003. We are grateful to the DFG for financial support (SPP1166: “lanthanide-specific functionalities in molecule and material”) and acknowledge Prof. Dr. Boese and D. Bläser for collection of X-ray data and H. Bandmann for measurement of 500 MHz NMR spectra.

Publication History

  1. Issue published online: 22 FEB 2008
  2. Article first published online: 6 FEB 2008
  3. Manuscript Received: 29 OCT 2007

Funded by

  • DFG. Grant Number: SPP1166

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Keywords:

  • calcium;
  • lanthanides;
  • metallocenes;
  • redox chemistry;
  • steric hindrance
Thumbnail image of graphical abstract

Unexpected attraction between extremely bulky cyclopentadienyl ligands of opposite chirality has been observed in perarylated metallocenes [(Ar5C5)2M]. The exceptional stability of such sterically congested metallocenes (see structure) is explained by a merry-go-round C[BOND]H⋅⋅⋅C(π) hydrogen-bond network. This stabilizing force even enables spontaneous reduction of a SmIII precursor to a SmII metallocene.

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