Transition metal and lanthanide cluster complexes constructed with thiacalix[n]arene and its derivatives
Transition metal and lanthanide cluster complexes constructed with thiacalix[n]arene and its derivatives
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DOI：
10.1016/j.ccr.2007.01.001
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发表时间：
2007-07-01
影响因子：
20.6
通讯作者：
Yamashita, Masahiro
中科院分区：
文献类型：
--
作者：
Kajiwara, Takashi;Iki, Nobuhiko;Yamashita, Masahiro
本文综述了硫杯[n]芳烃及其氧化衍生物亚磺酰杯[4]芳烃和磺酰杯[4]芳烃负载过渡金属和稀土簇合物的形成、结构和性质。每个硫杂杯[n]芳烃在环状骨架(-S-、-SO-或-SO2-)上都有施主原子(苯酚氧原子)，并以多齿多核配体的形式支持苯氧基桥联簇核的形成。对于第一排过渡金属，杯[4]芳烃提供了一个通过四个面三齿配位组装金属离子的平台，并形成了平面三核和四核簇合物。一个更大、更灵活的硫杂杯[6]芳烃可以结合多达5个金属离子在它采用挤压锥形构象时形成的配位空穴内。磺酰杯[4]芳烃通过苯氧基和磺酰氧供体对稀土离子表现出很强的亲和力，并通过控制合成条件生成了包括二核、四核、八核和十二核在内的各种簇合物。(C)2007 Elsevier B.V.保留所有权利。
This review deals with the formations, structures, and properties of transition metal and lanthanide clusters supported by thiacalix[n]arene and its oxidized derivatives, sulfinylcalix[4]arene and sulfonylcalix[4]arene. Each thiacalix[n]arene possesses donor atoms both on the lower rim position (phenol oxygen atoms) and on the cyclic framework itself (-S-, -SO-, or -SO2-), and behaves as a multidentate multi-nucleating ligand to support the formation of a phenoxo-bridged cluster core. For first row transition metals, calix[4]arenes offer a platform for assembling the metal ions via four fac-tridentate coordination sites, and planar tri- and tetra-nuclear clusters are formed. A larger and more flexible thiacalix[6]arene could bind up to five metal ions inside the coordination cavity formed when it adopts the pinched cone conformation. Sulfonylcalix[4]arene shows a strong affinity to lanthanide ions through phenoxo and sulfonyl oxygen donors, and yields a variety of cluster compounds involving di-, tetra-, octa-, and dodeca-nuclear cores, achieved by controlled synthetic conditions. (C) 2007 Elsevier B.V. All rights reserved.