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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Reducing zirconium(IV) phthalocyanines and the structure of a Pc4-Zr complex
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Reducing zirconium(IV) phthalocyanines and the structure of a Pc4-Zr complex

机译：还原锆（IV）酞菁和Pc4-Zr配合物的结构

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摘要

The synthesis and characterization of the ring-unsubstituted zirconium phthalocyanine PcZrCl2 (1; Pcx- = phthalocyaninato(x-)) and its reduction products are described. X-ray analysis of 1 (crystallized from hot 1-chloronaphthalene) reveals that 1 is a chloride-bridged dimer [PcZrCl](2)(mu-Cl)(2) in the solid-state; 1 was also characterized by UV-vis/MCD spectroscopy and cyclic voltammetry, which indicated reduction potentials at -0.55, -0.95 and -1.28 V. Although attempts to access these Pc-ring reduced species with KC8 led to mixtures of reduced products due to the insolubility of both starting materials, one equivalent of the reducing agent KEt3BH reacted with 1 to generate Pc3--containing species, as indicated by visible Q-band spectral changes (from lambda(max) = 686 for 1 to 589/611 nm), a single ESR peak (g = 2.001) and paramagnetically shifted H-1 NMR resonances consistent with the presence of a Pc-radical anion. Addition of two equivalents of KEt3BH to 1 generated Pc4--containing species, confirmed by a shift in lambda(max) to 522 nm and upfield-shifted H-1 NMR peaks relative to 1. Reaction of 1 with one and two equivalents of LiCp* did not generate Cp*-substituted products but also effected reduction to analogous Pc-3 and Pc-4 species. This latter material, the air-sensitive ring di-reduced "ate"-complex Pc4-Zr(LiCl)(1.5)(DME)(3), of the form [LiCl(DME)(4)](0.5)[Pc4-ZrClLi(DME)] was structurally characterized, illustrating partial bond localization in the Pc4- ring, which also adopts a saddle-shape vs. the more typical dome-configuration found in 1. This represents a rare example of an isolated and structurally characterized Pc4- complex.
机译：描述了环未取代的锆酞菁锆PcZrCl2（1; Pcx- =酞菁萘（x-））及其还原产物的合成和表征。 X射线分析1（从热的1-氯萘中结晶）显示1是固态的氯桥连二聚体[PcZrCl]（2）（mu-Cl）（2）; UV-vis / MCD光谱和循环伏安法还对1进行了表征，这表明还原电位为-0.55，-0.95和-1.28V。尽管尝试通过KC8接近这些Pc环还原物种，但由于两种原材料的不溶性，一当量的还原剂KEt3BH与1反应生成含Pc3的物质，如可见Q波段光谱变化所指示（从lambda（max）= 686表示1到589/611 nm） ，单个ESR峰（g = 2.001）和顺磁性转移的H-1 NMR共振与Pc自由基阴离子的存在一致。将两个当量的KEt3BH加到1个生成的含Pc4的物质中，这是通过将λ（max）移至522 nm以及相对于1的高场位移H-1 NMR峰证实的。1与一和两个当量的LiCp反应*不会产生Cp *取代的产物，但也会还原为类似的Pc-3和Pc-4物质。后一种材料是空气敏感环，其还原形式为[LiCl（DME）（4）]（0.5）[Pc4]，呈“ ate”字样的复杂的Pc4-Zr（LiCl）（1.5）（DME）（3）。 -ZrClLi（DME）]的结构表征，显示了Pc4-环中的部分键定位，该环也采用鞍形，而不是图1中发现的更典型的圆顶结构。这是一个罕见的分离并结构表征的例子PC4-复合物。

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