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
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- English
- Classification
- Chemistry
- License
- License undefined
- Identifiers
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- RERO DOC 27961
- DOI 10.1021/om2006479
- Persistent URL
- https://folia.unifr.ch/unifr/documents/302021
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