Coinage metal metallacycles involving a fluorinated 3,5-diarylpyrazolate
Coinage metal metallacycles involving a fluorinated 3,5-diarylpyrazolate
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DOI：
10.1039/d0nj03744c
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发表时间：
2020-09
影响因子：
3.3
通讯作者：
J. S. Lakhi;Monika R. Patterson;H. V. Rasika Dias
中科院分区：
文献类型：
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作者：
J. S. Lakhi;Monika R. Patterson;H. V. Rasika Dias
以含氟3，5-二芳基吡唑3，5-（3，5-（CF 3）2 Ph）2 PzH为原料，分别与氧化铜和银（I）反应，合成了铜（I）和银（I）吡唑配合物{[3，5-（3，5-（CF 3）2 Ph）2Cu}3和{[3，5-（3，5-（CF 3）2 Ph）2 Pz]Ag}3。通过Au（THT）Cl与[3，5-（3，5-（CF 3）2 Ph）2 Pz]H/NaH反应得到金（I）类似物。X射线衍射分析表明，钴配合物{[3，5-（3，5-（CF 3）2 Ph）2 Pz]M}3（M = Cu，Ag，Au）在固态下为三核配合物。它们具有扭曲的九元M3 N6金属环核。M-N距离遵循Cu < Au < Ag，这是从相应的钴金属离子的共价半径预期的趋势。3，5-（3，5-（CF 3）2 Ph）2 PzH在固态下形成氢键合的三聚体，其通过芳环之间的π-堆叠进一步组织。固体样品{[3，5-（3，5-（CF 3）2 Ph）2 Pz]M}3显示蓝色光致发光。铜配合物{[3，5-（3，5-（CF 3）2 Ph）2 Pz]Cu}3是介导叠氮-炔环加成反应的优良催化剂。
Copper(I) and silver(I) pyrazolate complexes {[3,5-(3,5-(CF3)2Ph)2Pz]Cu}3 and {[3,5-(3,5-(CF3)2Ph)2Pz]Ag}3 have been synthesized using the fluorinated 3,5-(diaryl)pyrazole 3,5-(3,5-(CF3)2Ph)2PzH and copper(I) oxide and silver(I) oxide, respectively. The gold(I) analog was obtained from a reaction between Au(THT)Cl and [3,5-(3,5-(CF3)2Ph)2Pz]H/NaH. The X-ray crystal structures show that the coinage metal complexes {[3,5-(3,5-(CF3)2Ph)2Pz]M}3 (M = Cu, Ag, Au) are trinuclear in the solid state. They feature distorted nine-membered M3N6 metallacyclic cores. The M–N distances follow Cu < Au < Ag, which is the trend expected from covalent radii of the corresponding coinage metal ions. The 3,5-(3,5-(CF3)2Ph)2PzH forms hydrogen bonded trimers in the solid state that are further organized by π-stacking between aryl rings. Solid samples of {[3,5-(3,5-(CF3)2Ph)2Pz]M}3 display blue photoluminescence. The copper complex {[3,5-(3,5-(CF3)2Ph)2Pz]Cu}3 is an excellent catalyst for mediating azide–alkyne cycloaddition chemistry.