Xu Qing-Dou, Zeng Chen, Su Shao-Dong, He Yong, Liu Yang, Hu Sheng-Min, Wu Xin-Tao, Sheng Tian-Lu
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, P.R. China.
School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing, 100049, P.R. China.
Dalton Trans. 2022 Sep 20;51(36):13938-13948. doi: 10.1039/d2dt01313d.
To investigate the electron transfer properties between metal centers and their influencing factors in binuclear and trinuclear cyanido-bridged mixed valence complexes with /-configuration, binuclear -[Cp(dppe)Fe(μ-NC)Ru(5,5'-dmbpy)(μ-CN)][PF] (cis-1[PF6]n, = 1, 2) and trinuclear /-[Cp(dppe)Fe(μ-NC)Ru(5,5'-dmbpy)(μ-CN)Fe(dppe)Cp][PF] (cis/trans-2[PF6]n, = 2, 3, 4) (Cp = 1,3-cyclopentadiene, dppe = 1,2-bis(diphenylphosphino)ethane, 5,5'-dmbpy = 5,5'-dimethyl-2,2'-bipyridyl) cyanido-bridged complexes were synthesized and well characterized. The experimental results indicate that the presence of the other terminal fragment Cp(dppe)Fe in cis-2[PF6]4 results in higher MMCT energy than that of cis-1[PF6]2. In addition, the -configuration is more conducive to electron transfer between metal centers than the -configuration in trinuclear cyanido-bridged mixed valence complexes. Moreover, these mixed valence complexes cis-1[PF6]2 and cis/trans-2[PF6]n ( = 3, 4) could be assigned to Class II systems according to Robin and Day.
为了研究具有/-构型的双核和三核氰基桥联混合价配合物中金属中心之间的电子转移性质及其影响因素，合成并充分表征了双核-[Cp(dppe)Fe(μ-NC)Ru(5,5'-dmbpy)(μ-CN)][PF]（顺式-1[PF6]n，n = 1, 2）和三核/-[Cp(dppe)Fe(μ-NC)Ru(5,5'-dmbpy)(μ-CN)Fe(dppe)Cp][PF]（顺式/反式-2[PF6]n，n = 2, 3, 4）（Cp = 1,3-环戊二烯，dppe = 1,2-双（二苯基膦基）乙烷，5,5'-dmbpy = 5,5'-二甲基-2,2'-联吡啶）氰基桥联配合物。实验结果表明，顺式-2[PF6]4中另一个末端片段Cp(dppe)Fe的存在导致MMCT能量高于顺式-1[PF6]2。此外，在三核氰基桥联混合价配合物中，/-构型比-构型更有利于金属中心之间的电子转移。而且，根据罗宾和戴的分类，这些混合价配合物顺式-1[PF6]2和顺式/反式-2[PF6]n（n = 3, 4）可归为II类体系。
