Ligand redox non-innocent behaviour in ruthenium complexes of ethynyl tolans

A small series of half-sandwich bis(phosphine) ruthenium acetylide complexes [Ru(CCC6H4CCSiMe3)(L2)Cp′] and [Ru(CCC6H4CCC6H4R-4)(L2)Cp′] (R = OMe, Me, CO2Me, NO2; L2 = (PPh3)2, Cp′ = Cp; L2 = dppe; Cp′ = Cp∗) have been synthesised. One-electron oxidations of these complexes gave the corresponding radical cations, which were significantly more chemically stable in the case of the Ru(dppe)Cp∗ derivatives. The representative complex [Ru(CCC6H4CCC6H4OMe-4)(dppe)Cp∗] was further examined by spectroelectrochemical (IR and UV–Vis–NIR) methods. The results of the spectroelectrochemical studies, supported by DFT calculations, indicate that the hole is largely supported by the ‘RuCCC6H4’ moiety in a manner similar to that described previously for simple aryl ethynyl complexes, rather than being more extensively delocalized along the entire conjugated ligand

Recent developments in chemistry, coordination, structure and biological aspects of 1-(acyl/aroyl)-3-(substituted) thioureas

1-(Acyl/aroyl)-3-(substituted)thioureas are privileged architectures that have received remarkable attention of researchers in view of their variable topological aspects, binding modes and broad spectrum promising pharmacological properties. Reactivity of acyl thiourea derivatives has presented various organic transformations into other demanding scaffolds and this is an attractive strategy for synthetic chemists to access heterocyclic cores. Multiple binding sites make them flexible ligands for complexation with transition metals thus occupying a distinct position in coordination chemistry. 1-(Acyl/aroyl)-3-(substituted)thioureas have also emerged as attractive candidates in various fields such as ion sensors, corrosion inhibitors, molecular electronics, in metal extraction and in pharmaceuticals. The medicinal chemistry of this organo-sulfur framework and the derived metal complexes has witnessed fantastic progress in the current era. In continuation of our efforts to compile data on the structural aspects and numerous applications of 1-(acyl/aroyl)-3-(substituted)thiourea analogs, continuous advances have prompted us to present an overview of the last 2 years literature on this exciting family of compounds through this review article.Fil: Saeed, Aamer. Quaid-i-Azam University; PakistánFil: Qamar, Rabia. Quaid-i-Azam University; PakistánFil: Fattah, Tanzeela Abdul. Quaid-i-Azam University; PakistánFil: Flörke, Ulrich. Universität Paderborn; AlemaniaFil: Erben, Mauricio Federico. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentin