Petrov Andrey V, Zagidullin Almaz A, Bezkishko Ilya A, Khrizanforov Mikhail N, Kholin Kirill V, Gerasimova Tatiana P, Ivshin Kamil A, Shekurov Ruslan P, Katsyuba Sergey A, Kataeva Olga N, Budnikova Yulia H, Miluykov Vasili A
Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov Str. 8, Kazan, Russia.
Dalton Trans. 2020 Dec 15;49(47):17252-17262. doi: 10.1039/d0dt03281f.
The reaction between aryl substituted sodium 1,2,3-triphospholides or disodium bis(1,2,3-triphospholide) and [Fe(η6-(C6H5CH3)Cp]+[PF6]- in boiling diglyme results in pure 1,2,3-triphosphaferrocenes 1-3 or bis(1,2,3-triphosphaferrocene) 4, respectively, in good yields. The structure of all obtained 1,2,3-triphosphaferrocenes 1-4 has been extensively studied experimentally (NMR, UV-Vis spectroscopy, and X-ray analysis for 1 and 4) and quantum chemically. The electrochemical properties of 1,2,3-triphosphaferrocenes 1-4 in the solid state were studied for the first time and a reversible one-electron oxidation (E1/2 = 0.52-0.92 V vs. Fc+/Fc) was demonstrated for 1, 3, and 4. In the case of 1,4-bis(5-phenyl-4-(1,2,3-triphospaferrocenyl))benzene 4, consecutive oxidation in the solid state is observed in contrast to other 1,2,3-triphosphaferrocenes 1-3. According to the ESR data, the g-factor of the oxidized bis(1,2,3-triphosphaferrocene), 4 (g = 2.12) is different from the g-factors of oxidized 1,2,3-triphosphaferrocenes 1-3 (g = 2.01). This is the first example of multi(ferrocenyl) systems based on the phosphaferrocene motif, which in turn opens up a new fundamental platform for the preparation of compounds with stimuli-responsive properties.
芳基取代的1,2,3 - 三磷杂环戊二烯钠或双（1,2,3 - 三磷杂环戊二烯）二钠与[Fe(η6-(C6H5CH3)Cp]+[PF6]-在沸腾的二甘醇二甲醚中反应，分别以良好的产率生成纯的1,2,3 - 三磷杂二茂铁1 - 3或双（1,2,3 - 三磷杂二茂铁）4。所有得到的1,2,3 - 三磷杂二茂铁1 - 4的结构都已通过实验（对1和4进行核磁共振、紫外 - 可见光谱和X射线分析）和量子化学方法进行了广泛研究。首次研究了1,2,3 - 三磷杂二茂铁1 - 4在固态下的电化学性质，结果表明1、3和4发生了可逆的单电子氧化（相对于Fc+/Fc，E1/2 = 0.52 - 0.92 V）。对于1,4 - 双（5 - 苯基 - 4 - （1,2,3 - 三磷杂二茂铁基））苯4，与其他1,2,3 - 三磷杂二茂铁1 - 3相比，在固态下观察到了连续氧化。根据电子顺磁共振数据，氧化后的双（1,2,3 - 三磷杂二茂铁）4的g因子（g = 2.12）与氧化后的1,2,3 - 三磷杂二茂铁1 - 3的g因子（g = 2.01）不同。这是基于磷杂二茂铁基序的多（二茂铁基）体系的首个例子，这反过来为制备具有刺激响应特性的化合物开辟了一个新的基础平台。
