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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Construction of di- and tetra-ferrocenyl spiroborate complexes from catechol building blocks and their redox behaviors
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Construction of di- and tetra-ferrocenyl spiroborate complexes from catechol building blocks and their redox behaviors

机译：从邻苯二酚结构单元构建二铁茂铁和四铁茂铁螺硼酸酯络合物及其氧化还原行为

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摘要

In this paper, we report a method for the construction of multi-ferrocenyl spiroborate assemblies from discrete mono- and di-ferrocenyl complexes. To prepare the building blocks for the spiroborate assemblies, 4-ferrocenylveratrole (1) and 4,5-diferrocenylveratrole (3) were first synthesized by Negishi crosscoupling between ferrocene and the corresponding aryl halides. Compounds 1 and 3 were characterized by NMR and UV-vis spectroscopies and electrochemical methods, namely cyclic voltammetry and differential pulse voltammetry. The potential splittings of 167 and 263 mV for the oxidations of the two ferrocenyl groups of 3 in CH_2Cl_2-n-Bu_4NPF_6 and n-Bu_4NB(C_6F_5)_4, together with the presence of an intervalence charge-transfer transition of 3+ in the NIR region, indicate a strong inter-ferrocenyl interaction through the ortho connection in the veratrole bridge. The treatment of 1 and 3 with BBr3, followed by complexation with B(OH)_3 in the presence of KOH, afforded potassium salts of di- and tetraferrocenyl spiroborate assemblies, K2 and K4, respectively. The spiroborate assemblies K2 and K4 were characterized by NMR and UV-vis spectroscopies, ESI-MS, and electrochemical methods. K2 exhibited a potential splitting value of 302 mV in DMF-n-Bu_4NPF_6, indicating electronic interactions over the boron center. K4 exhibited four one-electron-oxidation waves in DMF-n-Bu_4NPF_6 and n-Bu_4NB(C_6F_5)_4; the oneelectron- oxidized species 4 is thermodynamically more stable than 4~+ and 4~(2+). The overall E_(1/2)~1-E_(1/2)~4 spread for K4 is 201 mV larger than the E_(1/2)~1-E_(1/2)~2 splitting for 3 in DMF-n-Bu_4NPF_6, indicating that the spiroborate link between diferrocenyl units led to electronic interactions over the boron center.
机译：在本文中，我们报告了一种从离散的单-和二-二茂铁基配合物构造多二茂铁二茂铁硼酸酯组装体的方法。为了制备螺硼酸酯组件的结构单元，首先通过二茂铁与相应的芳基卤化物之间的Negishi交联来合成4-二茂铁基藜芦（1）和4,5-二茂铁基藜芦（3）。通过NMR和UV-可见光谱法以及电化学方法，即循环伏安法和差分脉冲伏安法，对化合物1和3进行表征。 CH_2Cl_2-n-Bu_4NPF_6和n-Bu_4NB（C_6F_5）_4中3个两个二茂铁基的氧化反应的电位分裂分别为167和263 mV，并且在NIR中存在3+的间隔电荷转移跃迁区域，表明通过四氢呋喃桥中的邻位连接具有强的二茂铁基相互作用。用BBr 3处理1和3，然后在KOH存在下与B（OH）3络合，分别得到二和四铁茂铁螺硼酸酯组装体的钾盐，K 2和K 4。通过NMR和UV-可见光谱，ESI-MS和电化学方法表征螺硼酸酯组装体K2和K4。 K2在DMF-n-Bu_4NPF_6中显示出302 mV的电势分裂值，表明在硼中心发生了电子相互作用。 K4在DMF-n-Bu_4NPF_6和n-Bu_4NB（C_6F_5）_4中表现出四个单电子氧化波;单电子氧化物种4在热力学上比4〜+和4〜（2+）更稳定。 K4的总E_（1/2）〜1-E_（1/2）〜4扩展比DMF中3的E_（1/2）〜1-E_（1/2）〜2分裂大201 mV -n-Bu_4NPF_6，表明二铁茂铁单元之间的螺硼酸酯键导致硼中心发生电子相互作用。

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