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Different Degrees of Electron Delocalization in Mixed Valence Ru‐Ru‐Ru Compounds by Cyanido‐/Isocyanido‐Bridge Isomerism
Author(s) -
Yang YuYing,
Zhu XiaoQuan,
Hu ShengMin,
Su ShaoDong,
Zhang LinTao,
Wen YueHong,
Wu XinTao,
Sheng TianLu
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201806157
Subject(s) - delocalized electron , chemistry , valence (chemistry) , electron delocalization , isocyanide , ruthenium , crystallography , cyanide , medicinal chemistry , stereochemistry , catalysis , inorganic chemistry , organic chemistry
The two stable pairs of trimetallic compounds trans ‐[Cp*(dppe)Ru(μ‐NC)Ru(dmap) 4 (μ‐CN)Ru(dppe)Cp*][PF 6 ] n ( 1 [PF 6 ] 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*][PF 6 ] n ( 2 [PF 6 ] n , n =2, 3), which demonstrate cyanide/isocyanide isomerism, have been synthesized and fully characterized. 1 3+ [PF 6 ] 3 and 2 3+ [PF 6 ] 3 are the one‐electron oxidation products of 1 2+ [PF 6 ] 2 and 2 2+ [PF 6 ] 2 , respectively. The results suggest that 1 [PF 6 ] 3 is a class III mixed valence compound, whereas 2 [PF 6 ] 3 might be an unusually symmetrical class II–III mixed valence compound composed of the two asymmetrical delocalized Ru III −NC−Ru II mixed valence subunits.