Syntheses and characterization of cyano-bridged homo and hetero bimetallic complexes containing η5 and η6-cyclic hydrocarbons

The reactions of [(ind)Ru(PPh3)2CN] (ind = η5-C9H7) (1) and [CpRu(PPh3)2CN] (Cp = η5-C5H5) (2) with [(η6-p-cymene)Ru(bipy)Cl]Cl (bipy = 2,2′-bipyridine) (3) in the presence of AgNO3/NH4BF4 in methanol, respectively, yielded dicationic cyano-bridged complexes of the type [(ind)(PPh3)2Ru(μ-CN)Ru(bipy)(η6-p-cymene)](BF4)2 (4) and [Cp(PPh3)2Ru(μ-CN)Ru(bipy)(η6-p-cymene)](BF4)2 (5). The reaction of [CpRu(PPh3)2CN] (2), [CpOs(PPh3)2CN] (6) and [CpRu(dppe)CN] (7) with the corresponding halide complexes and [(η6-p-cymene)RuCl2]2 formed the monocationic cyano-bridge complexes [Cp(PPh3)2Ru(μ-CN)Os(PPh3)2Cp](BF4) (8), [Cp(PPh3)2Os(μ- CN)Ru(PPh3)2Cp](BF4) (9) and [Cp(dppe)Ru(μ-CN)Os(PPh3)2Cp](BF4) (10) along with the neutral complexes [Cp(PPh3)2Ru(μ-CN)Ru (η6-p-cymene)Cl2] (11), [Cp(PPh3)2Os(μ-CN)Ru(η6-p-cymene)Cl2] (12), and [Cp(dppe) Ru(μ-CN)Ru(η6-p-cymene)Cl2] (13). These complexes were characterized by FT IR, 1H NMR, 31P{1H} NMR spectroscopy and the molecular structures of complexes 4, 8 and 11 were solved by X-ray diffraction studies.

Graphical abstractA number of cyano-bridged homo- and hetero-cyclic bimetallic complexes have been synthesized having cyclopentadienyl and indenyl ligands coordinated on to arene ruthenium and arene osmium systems. Some representative complexes are characterized by single crystal X-ray studies.Figure optionsDownload full-size imageDownload as PowerPoint slide