Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 57, Issue 43, Pages 14046-14050Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201806157
Keywords
class II-III; class III; CN ligands; cyanido-isocyanido isomerism; electron transfer
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Funding
- National Science Foundation of China [21773243]
- 973 Program [2014CB845603]
- Strategic Priority Research Program of the Chinese Academy of Sciences [XDB20010200]
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The two stable pairs of trimetallic compounds trans-[Cp*(dppe)Ru(-NC)Ru(dmap)(4)(-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(-CN)Ru(dmap)(4)(-NC)Ru(dppe)Cp*][PF6](n) (2[PF6](n), n=2, 3), which demonstrate cyanide/isocyanide isomerism, have been synthesized and fully characterized. 1(3+)[PF6](3) and 2(3+)[PF6](3) are the one-electron oxidation products of 1(2+)[PF6](2) and 2(2+)[PF6](2), respectively. The results suggest that 1[PF6](3) is a classIII mixed valence compound, whereas 2[PF6](3) might be an unusually symmetrical classII-III mixed valence compound composed of the two asymmetrical delocalized Ru-III-NC-Ru-II mixed valence subunits.
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