Metal complexes with polymeric ligands: Chelation and metalloinitiation approaches to metal tris(bipyridine)containing materials
Metal complexes with polymeric ligands: Chelation and metalloinitiation approaches to metal tris(bipyridine)containing materials
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DOI：
10.1002/1099-0518(200012)38:1
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发表时间：
2000-01-01
影响因子：
--
通讯作者：
Smith, AP
中科院分区：
文献类型：
--
作者：
Fraser, CL;Smith, AP
描述了金属聚合物配体配合物的合成方法。简单联吡啶（bpy）衍生物及其相应金属配合物制备方法的发展，促进了它们作为引发剂和偶联剂在聚合物合成中的应用。在控制聚合反应中，配体试剂被用作引发剂，生成聚（2-R-2-恶唑啉）（R =甲基、乙基、苯基、十一基）、聚苯乙烯、聚甲基丙烯酸甲酯（PMMA）s、聚（epsilon -己内酯）s和聚乳酸s，在链的末端或中心有联吡啶螯合物。采用链偶联法制备了聚乙二醇大配体。对反应动力学进行了详细的研究，以确定每种反应类型在不同催化剂和反应条件下的范围和局限性。以CuBr/1,4,4,7,7,10-六甲基三乙基四胺为催化剂，采用原子转移自由基聚合法制备了bpyPMMA(n) （n = 1或2）。综述了其他配体和金属引发剂的动力学研究结果。这样制备的大配体与一种不稳定的金属离子Fe（II）配合，具有标准的方案。提供了选定的铁中心聚合物的紫外可见光谱数据，证实了目标聚合物铁配合物的生产。惰性金属Ru（II）被用作产生建筑多样性的模板；制备了从中心核出发的1 ~ 6链聚合物配合物，以及不同的异臂星产物。(C) 2000 John Wiley & Sons, Inc。
Synthetic approaches to metal complexes with polymeric ligands are described. The development of efficient methods for preparing simple bipyridine (bpy) derivatives and their corresponding metal complexes has facilitated their use as initiators and coupling agents in polymer syntheses. Ligand reagents were utilized as initiators in controlled polymerization reactions to form poly(2-R-2-oxazolines) (R = methyl, ethyl, phenyl, undecyl), polystyrenes, poly(methyl methacrylates) (PMMA)s, poly(epsilon -caprolactone)s, and poly(lactic acid)s with bipyridine chelates at the end or centers of the chains. Poly(ethylene glycol) macroligands were formed by a chain-coupling method. Detailed studies of reaction kinetics were performed to determine the scope and limitations of each reaction type with different catalysts and reaction conditions. These results are illustrated for bpyPMMA(n) (n = 1 or 2), which was prepared by atom transfer radical polymerization with a CuBr/1,4,4,7,7,10-hexamethyltriethylenetetraamine catalyst system. Results of the kinetics investigations performed with other ligands and metalloinitiators are summarized. Macroligands thus prepared were coordinated to a labile metal ion, Fe(II), with standard protocols. Ultraviolet-Visible spectral data for selected Fe-centered polymers are provided that cofirm the production of the targeted polymeric iron complex products. An inert metal, Ru(II), was used as a template for generating architectural diversity; polymeric complexes with one to six chains emanating from the central core, as well as different heteroarm star products, were prepared. (C) 2000 John Wiley & Sons, Inc.