Different Degrees of Electron Delocalization in Mixed Valence Ru-Ru-Ru Compounds by Cyanido-/Isocyanido-Bridge Isomerism.

Yang, Yu-Ying; Zhu, Xiao-Quan; Hu, Sheng-Min; Su, Shao-Dong; Zhang, Lin-Tao; Wen, Yue-Hong; Wu, Xin-Tao; Sheng, Tian-Lu

Yang, Yu-Ying; Zhu, Xiao-Quan; Hu, Sheng-Min; Su, Shao-Dong; Zhang, Lin-Tao; Wen, Yue-Hong; Wu, Xin-Tao; Sheng, Tian-Lu.

Afiliación

Yang YY; State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science, Fuzhou, Fujian, 350002, P.R. China.
Zhu XQ; School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing, 100049, P.R. China.
Hu SM; State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science, Fuzhou, Fujian, 350002, P.R. China.
Su SD; State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science, Fuzhou, Fujian, 350002, P.R. China.
Zhang LT; State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science, Fuzhou, Fujian, 350002, P.R. China.
Wen YH; School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing, 100049, P.R. China.
Wu XT; State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science, Fuzhou, Fujian, 350002, P.R. China.
Sheng TL; School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing, 100049, P.R. China.

Angew Chem Int Ed Engl ; 57(43): 14046-14050, 2018 Oct 22.

Article en En | MEDLINE | ID: mdl-30182522

ABSTRACT

ABSTRACT

The two stable pairs of trimetallic compounds trans-[Cp*(dppe)Ru(µ-NC)Ru(dmap)4 (µ-CN)Ru(dppe)Cp*][PF6 ]n (1[PF6 ]n , n=2, 3; Cp*=1,2,3,4,5-pentamethylcyclopentadiene; dppe=1,2-bis-(diphenylphosphino)ethane; dmap= 4-dimethylaminopyridine) and trans-[Cp*(dppe)Ru(µ-CN)Ru(dmap)4 (µ-NC)Ru(dppe)Cp*][PF6 ]n (2[PF6 ]n , n=2, 3), which demonstrate cyanide/isocyanide isomerism, have been synthesized and fully characterized. 13+ [PF6 ]3 and 23+ [PF6 ]3 are the one-electron oxidation products of 12+ [PF6 ]2 and 22+ [PF6 ]2 , respectively. The results suggest that 1[PF6 ]3 is a classâIII mixed valence compound, whereas 2[PF6 ]3 might be an unusually symmetrical classâII-III mixed valence compound composed of the two asymmetrical delocalized RuIII -NC-RuII mixed valence subunits.

Palabras clave

CN ligands; class II-III; class III; cyanido-isocyanido isomerism; electron transfer

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