Wen Hui-Min, Wang Jin-Yun, Zhang Li-Yi, Shi Lin-Xi, Chen Zhong-Ning
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China.
Dalton Trans. 2016 Jun 28;45(26):10620-9. doi: 10.1039/c6dt01654e.
Heterodimetallic Ru-Fe complexes (tppz)(PPh3)2RuL (L = C[triple bond, length as m-dash]CFc, ; C[triple bond, length as m-dash]C-C6H4-C[triple bond, length as m-dash]CFc), ; C[triple bond, length as m-dash]C-C6H4-C6H4-C[triple bond, length as m-dash]CFc, ) were synthesized by the reactions of (tppz)(PPh3)2RuCl (tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine) with ferrocence-acetylide ligands and characterized by ESI-MS, and (1)H and (31)P NMR spectroscopies. The structure of was determined by X-ray crystallography. The electrochemical studies show that compounds - possess two widely separated anodic peaks, ascribable to one-electron oxidation of Fc and Ru(II), respectively. This assignment is further corroborated by the results of UV-vis-NIR, XPS, and theoretical calculation studies. Compound exhibits significant RuFe metal-metal interactions across the Ru-C[triple bond, length as m-dash]C-Fc backbone. As revealed by electrochemical, spectroscopic and theoretical computational studies, one-electron oxidized species 2 is between the electronically delocalized and valence-trapped state and shows a typical Robin-Day class II mixed-valence behavior.
通过(tppz)(PPh₃)₂RuCl（tppz = 2,3,5,6 - 四(2 - 吡啶基)吡嗪）与二茂铁乙炔配体反应合成了异双核Ru - Fe配合物(tppz)(PPh₃)₂RuL（L = C≡CFc，](ClO₄)；C≡C - C₆H₄ - C≡CFc，](ClO₄)；C≡C - C₆H₄ - C₆H₄ - C≡CFc，](ClO₄)），并通过电喷雾电离质谱、¹H和³¹P核磁共振光谱进行了表征。通过X射线晶体学确定了的结构。电化学研究表明化合物⁻具有两个相距较远的阳极峰，分别归因于Fc和Ru(II)的单电子氧化。紫外 - 可见 - 近红外光谱、X射线光电子能谱和理论计算研究结果进一步证实了这一归属。化合物在Ru-C≡C - Fc主链上表现出显著的RuFe金属 - 金属相互作用。电化学、光谱和理论计算研究表明，单电子氧化物种₂处于电子离域和价态捕获状态之间，表现出典型的罗宾 - 戴II类混合价行为。
