Platinum(II) Complexes with Non-Innocent Ligands: Solid-Phase Synthesis, Redox Chemistry and Luminescence
Platinum(II) Complexes with Non-Innocent Ligands: Solid-Phase Synthesis, Redox Chemistry and Luminescence
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DOI：
10.1002/chem.200801288
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发表时间：
2008-01-01
影响因子：
4.3
通讯作者：
Reinhardt, Sven
中科院分区：
文献类型：
--
作者：
Heinze, Katja;Reinhardt, Sven
在许多情况下，描述具有开壳配体的过渡金属配合物的电子结构可能不是一件简单的事情，但它对于我们理解它们的光谱性质和反应活性是至关重要的。一个潜在的非无辜配体和一个氧化还原活性中心离子的配合物或两个类似的非无辜配体(如儿茶酚/半喹啉、氨基/氨基、α-二亚胺/α-二亚胺)的配合物已被广泛研究。[1，2]在这里，我们报道了一种苯酚取代的α-二亚胺配体[4-(吡啶-2-亚甲基)氨基]苯酚(HO-N\N‘)，它与氧化还原活性儿茶酚/半喹啉配体(CAT/SQ)一起在Plati-ACHTUNGUNTRENNUNN(II)配合物中获得了非无辜的性质。以HO-N‘和3，6-二叔丁基儿茶酸酯为末端配体，1，10-邻菲咯啉-5，6-二酸(O2phen)为末端/桥联配体，采用固相合成法合成了二亚胺儿茶酚-铂(II)配合物H-1、H-2和H-3。我们报道了固相合成金属络合物的原理以及配体的合成及其通过硅醚连接到聚苯乙烯/二乙烯基苯载体上的细节。[3]生成的聚合物呈深绿色，表明形成了固定化的铂(II)络合物。通过用氟离子裂解硅醚来实现络合物从载体上的解离。可溶性阴离子酚类取代络合物1±、2±和3±可产生明亮的绿松石溶液。加入醋酸得到深绿色、难溶的中性络合物H-1、H-2和
Describing the electronic structure of transition-metal complexes with open-shell ligands may not be a straightforward task in many cases; however, it is of fundamental importance for our understanding of their spectroscopic properties and their reactivity. Complexes with one potentially non-innocent ligand and a redox active central ion or complexes with two similar non-innocent ligands (eg catecholato/semiquinonato, amido/aminyl, α-diimine/α-diiminyl) have been extensively studied.[1, 2]Here, we report a phenol-substituted α-diimine ligand [4-(pyridine-2-ylmethylene)-amino] phenol (HO-N\N’), which acquires a non-innocent character in conjunction with redox active catecholato/semiquinonato ligands (cat/sq) in plati-ACHTUNGTRENNUNGnum (II) complexes. The diimine catecholato-platinum (II) complexes H-1, H-2 and H-3, with HO-N\N’and 3, 6-di-tert-butyl-catecholate as terminal ligands and 1, 10-phenanthroline-5, 6-diolate (O2phen) as terminal/bridging ligands, were obtained by solid-phase synthesis.[3] For comparison reasons the methylated complex Me-1 was prepared by solution methods (Scheme 1, for experimental details see Supporting Information). The principle of solid-phase synthesis of metal complexes as well as details of the ligand synthesis and its attachment to polystyrene/divinyl benzene support through a silyl ether linker has been reported by us.[3] The formation of immobilised platinum (II) complexes is indicated by an intense green colour of the resulting polymer. Liberation of the complexes from the support is achieved by cleaving the silyl ether with fluoride ions. The soluble anionic phenolatesubstituted complexes 1À, 2À and 3À produce bright turquoise solutions. Addition of acetic acid gives the deep green and poorly soluble neutral complexes H-1, H-2 and