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Ruthenium Complexes Bearing Bulky Pentasubstituted Cyclopentadienyl Ligands and Evaluation of [Ru(η5-C5Me4R)(MeCN)3][PF6] Precatalysts in Nucleophilic Allylic Substitution Reactions

  1. Hui-Jun Zhang1,2,
  2. Bernard Demerseman2,
  3. Zhenfeng Xi1,
  4. Christian Bruneau2

Article first published online: 4 JUN 2008

DOI: 10.1002/ejic.200800295

Issue

European Journal of Inorganic Chemistry

European Journal of Inorganic Chemistry

Volume 2008, Issue 20, pages 3212–3217, July 2008

Additional Information

How to Cite

Zhang, H.-J., Demerseman, B., Xi, Z. and Bruneau, C. (2008), Ruthenium Complexes Bearing Bulky Pentasubstituted Cyclopentadienyl Ligands and Evaluation of [Ru(η5-C5Me4R)(MeCN)3][PF6] Precatalysts in Nucleophilic Allylic Substitution Reactions. Eur. J. Inorg. Chem., 2008: 3212–3217. doi: 10.1002/ejic.200800295

Author Information

  1. 1

    Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, China, Fax: +86-10-62751708

  2. 2

    Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes 1, Catalyse et Organométalliques, Université de Rennes 1, 35042 Rennes Cedex, France, Fax: +33-2-23236939

Publication History

  1. Issue published online: 10 JUL 2008
  2. Article first published online: 4 JUN 2008
  3. Manuscript Received: 20 MAR 2008

Funded by

  • Ambassade de France in China
  • International Program of the Natural Science Foundation of China

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Keywords:

  • Allylation;
  • Cyclopentadienyl ligands;
  • Homogeneous catalysis;
  • Regio­selectivity;
  • Ruthenium;
  • Metallocenes

Abstract

[Ru(η5-C5Me4R)(MeCN)3][PF6] (R = CH2tBu, iPr, tBu, and CF3; 2–5) complexes were synthesized in two steps starting from the appropriate cyclopentadienes and RuCl3·3H2O. The fully substituted ruthenocenes [Ru(C5Me5)(C5Me4R*)], [Ru(C5Me5)(C5nPr4R*)] {R* = (1R,5S)-6,6-dimethylbicyclo[3.1.1]hept-2-en-2-yl} and [Ru(C5Me5)(C5nPr5)] were obtained by treating [Ru(C5Me5)Cl]4 with the corresponding cyclopentadienyllithium salts. Complexes 2–5 were evaluated as catalyst precursors for nucleophilic allylic substitution reactions, and the results were compared to those obtained with the [Ru(C5Me5)(MeCN)3][PF6] (1) precatalyst. The etherification of p-methoxyphenol with the typical aliphatic chlorohexene allylic substrate shows that the introduction of the bulky tert-butyl and trifluoromethyl groups into the tetramethylcyclopentadienyl ring results in a valuable enhancement in regioselectivity in favour of the branched allyl aryl ether.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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