Rhenium(V) oxo complexes with acetylacetone derived Schiff bases: structure and catalytic epoxidation |
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Authors: | Sachse Anna Mösch-Zanetti Nadia C Lyashenko Ganna Wielandt J Wolfram Most Kerstin Magull Jörg Dall'Antonia Fabio Pal Aritra Herbst-Irmer Regine |
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Institution: | Institut für Chemie, Karl-Franzens-Universit?t, Schubertstrasse 1, A-8010 Graz, Austria. |
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Abstract: | Substitution reactions of rhenium(V) oxo precursors ReOCl3(PPh3)2] or NBu4]ReOCl4] with the bidentate acetylacetone-derived ketoamine ligands APOH = 4-anilino-3-penten-2-one, DPOH = 4-2,6-dimethylanilino]-3-penten-2-one, and MTPOH = 4-2-(methylthio)anilino]-3-penten-2-one gave the complexes ReO(APO)Cl2(PPh3)] (1), ReO(DPO)Cl2(PPh3)] (2), and NBu4]ReOLCl3] (3, L = APO; 4, L = DPO; 5, L = MTPO), respectively. All complexes exhibit only one ketoamino chelate, independent of the amount of ligand added to the rhenium precursors. The complexes were characterized by 1H and 13C NMR spectroscopy. X-ray crystal structures of the complexes 1, 2, 4, and 5, including that of MTPOH, were determined, revealing the trans position of the two oxygen atoms and the trans-Cl,Cl conformation in 1 and 2, in contrast to most other rhenium complexes of this type where the cis-Cl,Cl conformation is observed. Coordination of the potentially tridentate ligand MTPOH in 5 is bidentate with a dangling thioether substituent. Compound 2 shows catalytic activity in the oxidation of cis-cyclooctene with tert-butylhydroperoxide. |
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