Synthesis,Structure, and Reactivity of a Tetranuclear Cerium(IV) Oxo Cluster Supported by the Kläui Tripodal Ligand [Co(η5‐C5H5){P(O)(OEt)2}3]− |
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| Authors: | Dr Guo‐Cang Wang Dr Yat‐Ming So Kang‐Long Wong Ka‐Chun Au‐Yeung Dr Herman H‐Y Sung Prof Ian D Williams Prof Wa‐Hung Leung |
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| Institution: | Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong (P. R. China), Fax: (+852)?2356‐1594 |
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| Abstract: | A tetranuclear CeIV oxo cluster compound containing the Kläui tripodal ligand Co(η5‐C5H5){P(O)(OEt)2}3]? (LOEt?) has been synthesized and its reactions with H2O2, CO2, NO, and Brønsted acids have been studied. The treatment of Ce(LOEt)(NO3)3] with Et4NOH in acetonitrile afforded the tetranuclear CeIV oxo cluster Ce4(LOEt)4O7H2] ( 1 ) containing an adamantane‐like {Ce4(μ2‐O)6} core with a μ4‐oxo ligand at the center. The reaction of 1 with H2O2 resulted in the formation of the peroxo cluster Ce4(LOEt)4(μ4‐O)(μ2‐O2)4(μ2‐OH)2] ( 2 ). The treatment of 1 with CO2 and NO led to isolation of Ce(LOEt)2(CO3)] and Ce(LOEt)(NO3)3], respectively. The protonation of 1 with HCl, ROH (R=2,4,6‐trichlorophenyl), and Ph3SiOH yielded Ce(LOEt)Cl3] ( 3 ), Ce(LOEt)(OR)3] ( 4 ), and Ce(LOEt)(OSiPh3)3] ( 5 ), respectively. The chloride ligands in 3 are labile and can be abstracted by silver(I) salts. The treatment of 3 with AgOTs (OTs?=tosylate) and Ag2O afforded Ce(LOEt)(OTs)3] ( 6 ) and 1 , respectively. The electrochemistry of the Ce‐LOEt complexes has been studied by using cyclic voltammetry. The crystal structures of complexes 1 – 5 have been determined. |
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| Keywords: | cerium clusters oxo tetravalent tripod ligands |
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