Reducing Zirconium(IV) Phthalocyanines and the Structure of a Pc4–Zr Complex
Reducing Zirconium(IV) Phthalocyanines and the Structure of a Pc4–Zr Complex
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还原锆 (IV) 酞菁和 PC4 的结构
DOI：
10.1039/c5dt01778e
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发表时间：
2015
期刊：
影响因子：
--
通讯作者：
D. B.
中科院分区：
文献类型：
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作者：
Zhou;W.; Platel;R. H.; Tasso;T. T.; Furuyama;T.; Kobayashi;N.; Leznoff;D. B.
介绍了无环取代的酞菁锆PcZrCl 2（1; Pcx− = phthalocyanatox −）及其还原产物的合成和表征。1的X射线分析（从热的1-氯萘中结晶）表明1在固态下是氯桥二聚体[PcZrCl]2（μ-Cl）2; 1还通过UV-vis/MCD光谱和循环伏安法进行了表征，其表明还原电位为-0.55，-0.95和-1.28 V。尽管由于两种起始材料的不溶性，用KC 8获得这些Pc环还原物质的尝试导致还原产物的混合物，一当量的还原剂KEt 3BH与1反应生成含Pc 3 −的物质，如可见的Q带光谱变化（从λmax = 686（1）到589/611 nm），单个ESR峰（g = 2.001）和顺磁位移的1H NMR共振所示，与Pc自由基阴离子的存在一致。向1中加入2当量的KEt 3BH产生了含Pc 4 −的物质，通过λmax向522 nm的位移和相对于1的高场位移1H NMR峰证实。1与1当量和2当量的LiCp* 反应不会生成Cp* 取代的产物，但也会还原成类似的Pc 3 −和Pc 4 −物质。后一种材料，气敏环双还原“ate”-复合物Pc 4 −Zr（LiCl）1.5（DME）3，形式为[LiCl（DME）4]0.5[Pc 4 −ZrClLi（DME）]，其结构特征表明Pc 4 −环中的部分键定位，它也采用了马鞍形，而不是1中发现的更典型的圆顶形构型。这代表了一个罕见的例子，一个孤立的和结构特征的Pc 4 −复合物。
The synthesis and characterization of the ring-unsubstituted zirconium phthalocyanine PcZrCl2 (1; Pcx− = phthalocyaninatox−) 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(μ-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 λmax = 686 for 1 to 589/611 nm), a single ESR peak (g = 2.001) and paramagnetically shifted 1H 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 λmax to 522 nm and upfield-shifted 1H 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 Pc3− and Pc4− 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.