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Modulating the steric, electronic, and catalytic properties of cp* ruthenium half-Sandwich complexes with β-diketiminato ligands

  • Phillips, Andrew D. Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), Switzerland - School of Chemistry and Chemical Biology, University College Dublin, Ireland
  • Thommes, Katrin Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), Switzerland
  • Scopelliti, Rosario Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), Switzerland
  • Gandolfi, Claudio Department of Chemistry, University of Fribourg, Switzerland
  • Albrecht, Martin School of Chemistry and Chemical Biology, University College Dublin, Ireland - Department of Chemistry, University of Fribourg, Switzerland
  • Severin, Kay Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), Switzerland
  • Schreiber, Dominique F. School of Chemistry and Chemical Biology, University College Dublin, Ireland
  • Dyson, Paul J. Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), Switzerland
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    24.10.2011
Published in:
  • Organometallics. - 2011, vol. 30, no. 22, p. 6119–6132
English Five different types of β-diketiminate ligands, bearing electron-donating to strongly electron-withdrawing substituents, were synthesized and used in the synthesis of Cp* ruthenium complexes (Cp* = η⁵-C₅Me₅). One series consists of complexes with a covalent RuIII–Cl bond, and the other series features a reduced RuII center, where the chloride is abstracted by treatment of the corresponding RuIII compounds with Zn or Mg. All compounds were characterized by single-crystal X-ray diffraction, UV–visible spectroscopy, and cyclic voltammetry. In the case of RuII complexes, solution NMR techniques provided key information regarding the electronic and structural differences induced by the different β-diketiminate ligands employed. Capitalizing on the facile reduction–oxidation cycle of the Cp* ruthenium β-diketiminato complexes, catalytic atom transfer radical addition (ATRA) and cyclization (ATRC) reactions were performed on relevant substrates. The turnover rates are strongly dependent on the type of β-diketiminate used, where ligands with electron-withdrawing substituents, i.e., trifluoromethyl groups, provided complexes that efficiently catalyze the addition of CCl₄ or toluenesulfonyl chloride to styrene. In contrast, complexes with electron-donating substituents on the β-diketiminate promoted efficient ATR cyclization of N-allyl-N-phenyltrichloroacetamide and 2,2,2-trichloroethyl ether. Thus, the overall product conversion and yield are dependent on matching the ligand substitution pattern of the catalyst to the type of substrate.
Faculty
Faculté des sciences et de médecine
Department
Département de Chimie
Language
  • English
Classification
Chemistry
License
License undefined
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Persistent URL
https://folia.unifr.ch/unifr/documents/302021
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