Influence of the CN Orientation on the Degree of Electron Delocalization of Ru-Ru-Ru Mixed-Valent Complexes

被引：1

作者：

Liu, Xiao-Lin ^{[1
,2
]}

Li, Yi ^{[1
]}

Xu, Qing-Dou ^{[1
]}

Yang, Yu-Ying ^{[1
]}

Fu, Jin-Hui ^{[1
]}

Wu, Xin-Tao ^{[1
]}

Sheng, Tian-Lu ^{[1
]}

机构：

[1] Chinese Acad Sci, Fujian Inst Res Struct Matter, State Key Lab Struct Chem, Fuzhou 350002, Fujian, Peoples R China

[2] Univ Chinese Acad Sci, Sch Chem Sci, Beijing 100049, Peoples R China

来源：

INORGANIC CHEMISTRY | 2022年 / 61卷 / 44期

基金：

中国国家自然科学基金;

关键词：

SOLVENT DYNAMICAL CONTROL; VIBRATIONAL TIME-SCALE; CHARGE-TRANSFER IVCT; CRYSTAL-STRUCTURES; POLYPYRIDINE COMPLEXES; BRIDGED COMPLEXES; RUTHENIUM; TRANSITION; IRON; REACTIVITY;

D O I：

10.1021/acs.inorgchem.2c01172

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Investigations on mixed-valent complexes in the Class II/ Class III frontier have been a particularly interesting issue due to their special electron delocalization. In this work, a pair of cyanidometal-/ isocyanidometal-bridged Ru-Ru-Ru compounds, cis-[Cp(dppe)Ru- B-Ru(dppe)Cp]2+ (B = NCRu(bpy)2CN, 12+; B = CNRu(bpy)2NC, 22+; Cp = 1,3-cyclopentadienyl, dppe = 1,2-bis(diphenlyphosphine)-ethane, bpy = 2,2 & PRIME;-bipyridine), and one-electron oxidized 13+ and 23+ were synthesized and well characterized. For the two-electron oxidized 14+ and 24+, their Fourier transform infrared (FTIR) and UV-vis-NIR spectra were investigated by employing spectroelectrochemical methods. The time-dependent density-functional theory (TDDFT) calculations and the experimental results indicate that the one-/two-electron oxidized mixed-valent compounds belong to Class II-III systems.

引用

页码：17392 / 17401

页数：10

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