Details

Autor(en) / Beteiligte

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

Titel

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

Ist Teil von

• Angewandte Chemie International Edition, 2018-10, Vol.57 (43), p.14046-14050

Auflage

International ed. in English

Ort / Verlag

Germany: Wiley Subscription Services, Inc

Erscheinungsjahr

2018

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• 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 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. Isomeric triruthenium mixed valence (MV) compounds 13+[PF6]3 and 23+[PF6]3 contain CN bridges with different orientations. Upon isomerization, compound 13+ undergoes a change in the orientation of its ligating CN groups and the electron density of the cyanidometal‐bridged MV complex becomes fully delocalized (class III). Compound 23+ is composed of two asymmetrically delocalized RuII−CN−RuIII units and it behaves like a class II–III cyanide‐bridged MV species.