The synthesis and structure of heteroleptic tris(diimine)ruthenium(II)complexes

摘要

The reactions of bidentate diimine ligands(L~2)with cationic bis(diimine)[Ru(L)(L~1)(CO)Cl]~4 complexes(L,L~1,L~2 are dissimilar diimine ligands),in the presence of trimethylamine-N-oxide(Me_3NO)as a decarbonylation reagent,lead to the formation of heteroleptic tris(diimine)ruthenium(II)complexes,[Ru(L)(L')(L~2)]~2+.Typically isolated as hexafluorophosphate or perchlorate salts,these complexes were characterised by UV-visible,infrared and mass spectroscopy,cyclic voltammetry,microanalyses and NMR spectroscopy.Single crystal X-ray studies have elucidated the structures of K[Ru(bpy)(phen)(4,4'-Me_2bpy)](PF_6)_3~1/2H_2O,[Ru(bpy)(5,6-Me_2phen)(Hdpa)](ClO4)2,[Ru(bpy)(phen)(5,6-Me_2phen)](ClO_4)_2,[Ru(bpy)(5,6'-Me_2phen)(4,4'-Me_2bpy)](PF_6)_2-EtOH,[Ru(4,4'-Me_2bpy)(phen)(Hdpa)](PF_6)_2-MeOH and[Ru(bpy)(4,4'-Me_2bpy)(Hdpa)](ClO_4)_2~1/2Hdpa(where Hdpa is di(2-pyridyl)amine).A novel feature of the first complex is the presence of a dinuclear anionic adduct,[K_2(PF_6)_6]~4 ,in which the two potassium centres are bridged by two fluorides from different hexafluorophosphate ions forming a K_2F_2 bridging unit and by two KFPFK bridging moieties.