Anodic Electrochemistry of Free and Coordinated 1,1‘-Bis(di-tert-butylphosphino)ferrocene
Anodic Electrochemistry of Free and Coordinated 1,1‘-Bis(di-tert-butylphosphino)ferrocene
复制标题
游离和配位1,1-双(二叔丁基膦)二茂铁的阳极电化学
DOI：
--
复制
发表时间：
2006
期刊：
影响因子：
--
通讯作者：
C. Nataro
中科院分区：
文献类型：
--
作者：
Fawn N. Blanco;Laura E. Hagopian;William R McNamara;J. Golen;A. Rheingold;C. Nataro
研究了1，1 '-双（二叔丁基膦基）二茂铁（dtbpf）在二氯甲烷中以六氟磷酸四丁基铵为支持电解质的电化学行为。制备了两种新的dtbpf与过渡金属键合的配合物，并进行了表征。这两个新的配合物以及两个以前报道的配合物进行了分析，通过循环伏安法。此外，还制备了硫属化合物dtbpfS 2和dtbpfSe 2，并通过NMR对其进行了表征，确定了dtbpfSe 2的结构。由于铁中心的存在，dtbpfS 2的氧化是一个简单的单电子过程。与此相反，dtbpfSe 2的氧化是电化学不可逆的，似乎进行EE机制。dtbpfSe 2的化学氧化导致形成[dtbpfSe 2][BF 4]2，其中形成Se-Se键。通过~（31）P NMR和X射线晶体学对其结构进行了表征。详细的电化学分析表明，dtbpfSe 2的氧化发生两个单独的。
The electrochemistry of 1,1‘-bis(di-tert-butylphosphino)ferrocene (dtbpf) was examined in methylene chloride with tetrabutylammonium hexafluorophosphate as the supporting electrolyte. Two new complexes in which dtbpf was bound to a transition metal were prepared and characterized. The two new complexes as well as two previously reported complexes were analyzed by cyclic voltammetry. In addition, the chalcogenids, dtbpfS2 and dtbpfSe2, were prepared and characterized by NMR and the structure of dtbpfSe2 was determined. The oxidation of dtbpfS2 is a simple one-electron process due to the presence of the iron center. In contrast, the oxidation of dtbpfSe2 is electrochemically irreversible and appears to proceed by an EE mechanism. Chemical oxidation of dtbpfSe2 resulted in the formation of [dtbpfSe2][BF4]2, in which a Se−Se bond formed. This compound was characterized by 31P NMR and X-ray crystallography. A detailed analysis of the electrochemistry suggests that the oxidation of dtbpfSe2 occurs by two separa...