Substituent-Induced Reactivity in Quinonoid-Bridged Dinuclear Complexes: Comparison between the Ruthenium and Osmium Systems
| Autor: | Michael G. Sommer, Biprajit Sarkar, David Schweinfurth, Fritz Weisser, Stephan Hohloch |
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| Rok vydání: | 2013 |
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| Zdroj: | Organometallics. 32:2069-2078 |
| ISSN: | 1520-6041 0276-7333 |
| DOI: | 10.1021/om300939x |
| Popis: | The ligand 2,5-bis[2-(methylthio)anilino]-1,4-benzoquinone (L) was used in its doubly deprotonated form to synthesize the complex [{Cl(η6-Cym)Os}2(μ-η2:η2-L-2H)] (1; Cym = p-cymene = 1-isopropyl-4-methylbenzene). Spectroscopic characterization and elemental analysis confirms the presence of the chloride ligands in 1, which indirectly shows that the bridging ligand L-2H acts in a bis-bidentate fashion in 1, with the thioether substituents on the bridge remaining uncoordinated. Abstraction of the chloride ligands in 1 by AgBF4 in CH3CN leads not only to the release of those chloride ligands but also to a simultaneous substituent-induced release of Cym with the bridging ligand changing its coordination mode to bis-tridentate. In the resulting complex [{(CH3CN)3Os}2(μ-η3:η3-L-2H)]2+ (22+), the thioether groups of L-2H are now coordinated to the osmium centers with the bridging ligand coordinating to the metal center in a bis-meridional form. The coordination mode of L-2H in 22+ was confirmed by single-crystal... |
| Databáze: | OpenAIRE |
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