University of Regensburg, Institute of Inorganic Chemistry, 93040 Regensburg, Germany.
Dalton Trans. 2018 Aug 14;47(32):11058-11069. doi: 10.1039/c8dt02003e.
The dinuclear ruthenium complex [CpRu(μ-C10H8)RuCp] (1; Cp* = η5-C5Me5) was prepared by reduction of the cationic precursor [CpRu(η6-C10H8)]PF6 with KC8. Diamagnetic 1 has a symmetric molecular structure with an anti-facial configuration of the CpRu moieties coordinating to naphthalene. Density Functional Theory (DFT) studies showed an electronic structure similar to that of the analogous diiron complex [CpFe(μ-C10H8)FeCp]. Cyclic voltammetry and UV-vis spectroelectrochemistry showed that 1 can be reversibly oxidized to 1+ and 12+. Chemical oxidation with [Cp2Fe]BArF4 afforded the paramagnetic compound [1]BArF4, which was investigated by EPR, single-crystal X-ray diffractometry and DFT calculations. Reaction of 1 with Brookhart's acid gave the hydride complex [3]BArF4, which was characterized spectroscopically and crystallographically. Cyclic voltammetry showed that [3]+ is converted back to 1 upon reduction and oxidation.
双核钌配合物 [CpRu(μ-C10H8)RuCp]（1；Cp*=η5-C5Me5）通过用 KC8 还原阳离子前体 [CpRu(η6-C10H8)]PF6 制备。顺磁性 1 具有对称的分子结构，CpRu 部分呈反式面构型，与萘配位。密度泛函理论（DFT）研究表明，其电子结构类似于类似的二铁配合物 [CpFe(μ-C10H8)FeCp]。循环伏安法和紫外可见光谱电化学表明，1 可被可逆地氧化为 1+和 12+。用 [Cp2Fe]BArF4 进行化学氧化得到顺磁性化合物 [1]BArF4，并用 EPR、单晶 X 射线衍射和 DFT 计算进行了研究。1 与 Brookhart 酸反应得到氢化物配合物 [3]BArF4，其光谱和晶体结构均有特征。循环伏安法表明，[3]+在还原和氧化时可转化回 1。
