title: Tetravalent cerium pseudohalide complexes supported by the Kläui tripodal ligand [Co(η5-C5H5){P(O)(OEt)2}3].
abstract: Cerium(iv) pseudohalide complexes supported by the Kläui tripodal ligand [Co(η5-C5H5){P(O)(OEt)2}3]-(LOEt-) have been synthesized and structurally characterized. The treatment of [CeIV(LOEt)2Cl2] (1) with 2 equivalents of [AgX] in acetonitrile afforded [CeIV(LOEt)2X2] [X-= NCS-(2), N3-(3), F-(4)]. The reaction of 1 with [AgCN] in dichloromethane at -40 °C led to formation of a bimetallic CeIV/AgIcyanide complex that decomposed in solution at room temperature. In the presence of BPh3, 1 reacted with [AgCN] to yield the cyanoborate complex [CeIV(LOEt)2(NCBPh3)2] (6) that is stable in solution. The chlorination of [CeIII(LOEt)2(NO3)] with PhICl2afforded [CeIV(LOEt)2(NO3)Cl] (7) that reacted with [AgCN] to yield the heterometallic CeIV/AgIcyanide complex [{Ce(LOEt)2(NO3)}2{μ-Ag(CN)2}][AgCl2] (8). The reaction of [CeIV(LOEt)Cl3] with [AgN3] afforded the tetranuclear CeIVoxo azido cluster [Ce4(LOEt)4(μ4-O)(μ2-O)2(μ2-N3)6] (9). The structures of complexes 2, 3, 6 and 9 have been established by X-ray crystallography.
authors: Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, People's Republic of China. chleung@ust.hk yatming.so@riken.jp.
authors: Ka-Chun
authors: KC
authors: Au-Yeung
authors: Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, People's Republic of China. chleung@ust.hk yatming.so@riken.jp.
authors: Yat-Ming
authors: YM
authors: So
authors: Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, People's Republic of China. chleung@ust.hk yatming.so@riken.jp.
authors: Herman H-Y
authors: HH
authors: Sung
authors: Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, People's Republic of China. chleung@ust.hk yatming.so@riken.jp.
authors: Ian D
authors: ID
authors: Williams
authors: Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, People's Republic of China. chleung@ust.hk yatming.so@riken.jp.
authors: Wa-Hung
authors: WH
authors: Leung