Synthesis and Characterisation of Novel Bis(diphenylphosphane oxide)methanidoytterbium(III) Complexes |
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Authors: | Shalini Rangarajan Owen A. Beaumont Maravanji S. Balakrishna Glen B. Deacon Victoria L. Blair |
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Affiliation: | 1.IITB-Monash Academy, Indian Institute of Technology Bombay, Mumbai 400076, India;2.School of Chemistry, Monash University, Melbourne 3800, Australia |
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Abstract: | Reaction of [YbCp2(dme)] (Cp = cyclopentadienyl, dme = 1,2 dimethoxyethane) with bis(diphenylphosphano)methane dioxide (H2dppmO2) leads to deprotonation of the ligand H2dppmO2 and oxidation of ytterbium, forming an extremely air-sensitive product, [YbIII(HdppmO2)3] (1), a six-coordinate complex with three chelating (OPCHPO) HdppmO2 ligands. Complex 1 was also obtained by a redox transmetallation/protolysis synthesis from metallic ytterbium, Hg(C6F5)2, and H2dppmO2. In a further preparation, the reaction of [Yb(C6F5)2] with H2dppmO2, not only yielded compound 1, but also gave a remarkable tetranuclear cage, [Yb4(µ-HdppmO2)6(µ-F)6] (2) containing two [Yb(µ-F)]2 rhombic units linked by two fluoride ligands and the tetranuclear unit is encapsulated by six bridging HdppmO2 donors. The fluoride ligands of the cage result from C-F activation of pentafluorobenzene and concomitant formation of p-H2C6F4 and m-H2C6F4, the last being an unexpected product. |
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Keywords: | ytterbium phosphine oxide methanide C-F activation fluoride cage |
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