Phenylcyanamidoruthenium Scorpionate Complexes

Nine [Ru(Tp)(dppe)L] complexes, where Tp is hydrotris(pyrazol-1-yl)borate, dppe is ethylenebis(diphenylphosphine), and L is (4-nitrophenyl)cyanamide (NO2pcyd–), (2-chlorophenyl)cyanamide (2-Clpcyd–), (3-chlorophenyl)cyanamide (3-Clpcyd–), (2,4-dichlorophenyl)cyanamide (2,4-Cl2pcyd–), (2,3-dichlorophenyl)cyanamide (2,3-Cl2pcyd–), (2,5-dichlorophenyl)cyanamide (2,5-Cl2pcyd–), (2,4,5-trichlorophenyl)cyanamide (2,4,5-Cl3pcyd–), (2,3,5,6-tetrachlorophenyl)cyanamide (2,3,5,6-Cl4pcyd–), and (pentachlorophenyl)cyanamide (Cl5pcyd–), and the dinuclear complex [{Ru(Tp)(dppe)}2(μ-adpc)], where adpc2– is azo-4,4-diphenylcyanamide, have been prepared and characterized. The crystal structures of [Ru(Tp)(dppe)(Cl5pcyd)] and [{Ru(Tp)(dppe)}2(μ-adpc)] reveal the RuII ion to occupy a pseudooctahedral coordination sphere in which the cyanamide ligand coordinates to RuII by its terminal nitrogen atom. For both complexes, the cyanamide ligands are planar, indicating significant π mixing between the cyanamide and phenyl moietie...