The synthesis, structure, reactivity and electrochemical properties of ruthenium complexes featuring cyanoacetylide ligands

The complex [Ru(CCCN)(dppe)Cp*] (1) is readily obtained (ca. 70%) from the sequential reaction of [Ru(CCH2)(dppe)Cp*]PF6 with nBuLi and phenyl cyanate. The complex behaves as a typical transition metal acetylide upon reaction with tetracyanoethene, affording a metallated pentacyanobutadiene. Complex 1 is a useful metalloligand, and its reactions with [W(thf)(CO)5], [RuCl(PPh3)2Cp], [RuCl(dppe)Cp*] or cis-[RuCl2(dppe)2] all afforded products featuring the M–CCCN–M′ motif, for which ground state structures indicate a degree of polarisation. Electrochemical and spectroelectrochemical studies reveal moderate interactions between the metal centres in the 35-electron dications [{Cp*(dppe)Ru}(μ-CCCN){RuL2Cp′}]2+ (RuL2Cp′ = Ru(PPh3)2Cp, Ru(dppe)Cp*).

The complex [Ru(CCCN)(dppe)Cp*] (1) is readily obtained (ca. 70%) from the sequential reaction of [Ru(CCH2)(dppe)Cp*]PF6 with nBuLi and phenyl cyanate. The complex is a useful metalloligand, and has been used in the preparation of complexes featuring the M–CCCN–M′ motif. Electrochemical and spectroelectrochemical studies reveal moderate interactions between the metal centres in the 35-electron dications [{Cp*(dppe)Ru}(μ-CCCN){RuL2Cp′}]2+ (RuL2Cp′ = Ru(PPh3)2Cp, Ru(dppe)Cp*).Figure optionsDownload as PowerPoint slide