Au-Yeung Ka-Chun, So Yat-Ming, Sung Herman H-Y, Williams Ian D, Leung Wa-Hung
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, People's Republic of China.
Dalton Trans. 2016 Nov 15;45(45):18163-18170. doi: 10.1039/c6dt03740b.
Cerium(iv) pseudohalide complexes supported by the Kläui tripodal ligand [Co(η-CH){P(O)(OEt)}] (L) have been synthesized and structurally characterized. The treatment of [Ce(L)Cl] (1) with 2 equivalents of [AgX] in acetonitrile afforded [Ce(L)X] [X = NCS (2), N (3), F (4)]. The reaction of 1 with [AgCN] in dichloromethane at -40 °C led to formation of a bimetallic Ce/Ag cyanide complex that decomposed in solution at room temperature. In the presence of BPh, 1 reacted with [AgCN] to yield the cyanoborate complex [Ce(L)(NCBPh)] (6) that is stable in solution. The chlorination of [Ce(L)(NO)] with PhICl afforded [Ce(L)(NO)Cl] (7) that reacted with [AgCN] to yield the heterometallic Ce/Ag cyanide complex [{Ce(L)(NO)}{μ-Ag(CN)}][AgCl] (8). The reaction of [Ce(L)Cl] with [AgN] afforded the tetranuclear Ce oxo azido cluster [Ce(L)(μ-O)(μ-O)(μ-N)] (9). The structures of complexes 2, 3, 6 and 9 have been established by X-ray crystallography.
由克劳伊三脚架配体[Co(η-CH){P(O)(OEt)}]（L）支撑的铈（IV）拟卤化物配合物已被合成并进行了结构表征。在乙腈中，用2当量的[AgX]处理[Ce(L)Cl]（1）得到[Ce(L)X] [X = NCS（2）、N（3）、F（4）]。在-40°C下，1与[AgCN]在二氯甲烷中反应生成一种双金属铈/银氰化物配合物，该配合物在室温下在溶液中分解。在BPh存在下，1与[AgCN]反应生成在溶液中稳定的氰硼酸根配合物[Ce(L)(NCBPh)]（6）。用PhICl对[Ce(L)(NO)]进行氯化得到[Ce(L)(NO)Cl]（7），其与[AgCN]反应生成异金属铈/银氰化物配合物[{Ce(L)(NO)}{μ-Ag(CN)}][AgCl]（8）。[Ce(L)Cl]与[AgN]反应得到四核铈氧叠氮簇[Ce(L)(μ-O)(μ-O)(μ-N)]（9）。配合物2、3、6和9的结构已通过X射线晶体学确定。
