Research Article

Organometallic Cerium Complexes from Tetravalent Coordination Complexes

  1. Polly L. Arnold1,
  2. Ian J. Casely1,
  3. Sergey Zlatogorsky1,
  4. Claire Wilson2

Article first published online: 24 NOV 2009

DOI: 10.1002/hlca.200900152

Issue

Helvetica Chimica Acta

Helvetica Chimica Acta

Volume 92, Issue 11, pages 2291–2303, November 2009

Additional Information

How to Cite

Arnold, P., Casely, I., Zlatogorsky, S. and Wilson, C. (2009), Organometallic Cerium Complexes from Tetravalent Coordination Complexes. Helvetica Chimica Acta, 92: 2291–2303. doi: 10.1002/hlca.200900152

Author Information

  1. 1

    School of Chemistry, Joseph Black Building, University of Edinburgh, West Mains Road, Edinburgh, EH9 3JJ, UK

  2. 2

    Rigaku Europe, Chaucer Business Park, Watery Lane, Sevenoaks, Kent, UK

Publication History

  1. Issue published online: 24 NOV 2009
  2. Article first published online: 24 NOV 2009
  3. Manuscript Received: 30 APR 2009

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Keywords:

  • Cerium complexes;
  • Salt metathesis;
  • Carbene complexes;
  • Alkoxides;
  • Lanthanide complexes

Graphical Abstract

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Abstract

The use of tetravalent cerium alkoxides, nitrates, and triflates was studied as a direct route to [CeIV(carbene)] complexes. Protonolysis reactions between 1H-imidazolium- or imidazoline (=4,5-dihydro-1H-imidazole)-containing alkoxide proligands HL (L=OCMe2CH2[1-C(NCHCHNiPr)]) and HLS (LS=OCMe2CH2[1-C(NCH2CH2NiPr)]) and CeIVtert-butoxide, triflate, and nitrate compounds were studied to target [CeIV(N-heterocyclic carbene)] complexes (of unsaturated and saturated carbenes, resp.). Instead, tetravalent cerium imidazolium [(OtBu)3Ce(μ-OtBu)2(μ-HL)Ce(OtBu)3], or imidazolinium adducts [(OtBu)3Ce(μ-OtBu)2(μ-HLS)Ce(OtBu)3] were isolated. However, the salt metathesis of cerium triflate with KL provided a simple route to [CeL4], which was significantly improved if an external oxidant, benzoquinone, was included in the mixture to maintain oxidation-state integrity. Likewise, the salt metathesis of cerium triiodide with KL and added benzoquinone provided a straightforward route to [CeL4].

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