Chemistry of coordinatively unsaturated organoruthenium amidinates as entry to homogeneous catalysis
| Autor: | Mitsuru Gondo, Hideo Kondo, Kazuma Miyazaki, Satoshi Masuda, Karl Kirchner, Yoshitaka Yamaguchi, Kouki Matsubara, Hideo Nagashima, Taizo Hayashida |
|---|---|
| Rok vydání: | 2003 |
| Předmět: |
Cationic polymerization
chemistry.chemical_element Homogeneous catalysis Photochemistry Redox Ruthenium Catalysis Inorganic Chemistry chemistry.chemical_compound chemistry Intramolecular force Polymer chemistry Materials Chemistry Lewis acids and bases Physical and Theoretical Chemistry Trimethylsilyldiazomethane |
| Zdroj: | Coordination Chemistry Reviews. 245:177-190 |
| ISSN: | 0010-8545 |
| DOI: | 10.1016/s0010-8545(03)00124-3 |
| Popis: | The chemistry of coordinatively unsaturated organoruthenium complexes is reviewed in this article. In particular, the subject is focused on neutral and cationic organoruthenium amidinates, which formally have 16 valence electrons and show signs of coordinative unsaturation. The ruthenium amidinates, ( 5 -C5Me5)Ru(-amidinate) (1), and their isoelectronic analogues, [( 6 -arene)Ru(-amidinate)] + (2), are synthesized and characterized; a possible stabilizing factor of the unsaturated metal center is weak coordination of -electrons in the amidinates ligands. Reactions of various two-electron donor ligands with 1 or 2 reveal the strong -donor property of 1 and Lewis acid nature of 2. One or two-electron redox processes of 1 in the reactions with organic halides are studied by isolation of the corresponding Ru(III) and Ru(IV) products; the results lead to their catalysis for the Tsuji–Trost reaction and the intramolecular Kharasch reaction. The treatment of 2 with trimethylsilyldiazomethane results in the formation of cationic amidinato-carbene complexes, which involve unusual reversible metal-to-carbon silyl group migration. © 2003 Elsevier B.V. All rights reserved. |
| Databáze: | OpenAIRE |
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