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Different Degrees of Electron Delocalization in Mixed Valence Ru‐Ru‐Ru Compounds by Cyanido‐/Isocyanido‐Bridge Isomerism
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AbstractThe 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 class III mixed valence compound, whereas 2[PF6]3 might be an unusually symmetrical class II–III mixed valence compound composed of the two asymmetrical delocalized RuIII−NC−RuII mixed valence subunits.
Title: Different Degrees of Electron Delocalization in Mixed Valence Ru‐Ru‐Ru Compounds by Cyanido‐/Isocyanido‐Bridge Isomerism
Description:
AbstractThe 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 class III mixed valence compound, whereas 2[PF6]3 might be an unusually symmetrical class II–III mixed valence compound composed of the two asymmetrical delocalized RuIII−NC−RuII mixed valence subunits.
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