Syntheses And Characterization Of Ruthenium Complexes With Chiral Bi-and Tetra-dentate Schiff Base Ligands

Two asymmetric ruthenium complexes and five tetradentate Schiff base ruthenium complexes bearing PPh₃ ligands were synthesized from treatment of ruthenium starting materials[RuCl₂?PPh₃?₃],[RuHCl?CO??PPh₃?₃],[RuCl₃?NO??PPh₃?₂]or cis-[?bpy?₂RuCl₂·2H₂O]with chiral bidentate and tetradentate Schiff base ligands in this thesis.?1?21 chiral bidentate Schiff base ligands were obtained from reaction of salicylaldehyde,5-nitrosalicylaldehyde or 3,5-di-tert-butylsalicylaldehyde and chiral amines in molar ratio of 1:1 in ethanol.These ligands were well characterized by nuclear magnetic resonance?NMR?,infrared?IR?and ultraviolet?UV?spectroscopies.Since these kinds of ligands have the N,O atoms with strong coordination ability,so treatment of ruthenium startings[RuCl₃?NO??PPh₃?₂]or cis-[?bpy?₂RuCl₂·2H₂O]with two chiral bidentate Schiff baseligandsN-?2-hydroxy-3,5-dibromo-benzylidene?-?R?-?+?-?-methylbenzylamine?LNO*11?and N-?2-hydroxy-5-chloro-benzylidene?-?R?-?+?-2-amino-3-phenyl-1-propanol?LNO*10?resultedinformationofaacyl-rutheniumcomplex[Ru??²-C,O-salBr₂?Cl?NO??PPh₃?₂]and a cationic complex[Ru??²-O,O-salCl??bpy?₂]PF₆,whose molecular structures were unambiguously established by single-crystal X-ray diffraction.?2?ThreetetradentateSchiffbaseligands?N-?2-hydroxy-5-chlorobenzylidene??2-1,2-propanediamine?LN2O21*H?,?N-?2-Hydroxy-3,5-dibromo-benzylidene??2-1,2-propanediamine?LN2O22*H?,?N-?2-Hydroxy-benzylidene??2-1,2-propanediamine?LN2O23*H?were prepared from reaction of salicylaldehyde,5-chlorosalicylaldehyde or 3,5-dibromosalicylaldehyde and1,2-propanediamine in molar ratio of 1:2 in ethanol.Treatment of ruthenium starting materials[RuCl₂?PPh₃?₃]or[RuHCl?CO??PPh₃?₃]with three chiral bidentate Schiff base ligands LN2O21*H,LN2O22*H and LN2O23*H afforded five tetradentate ruthenium complexes[Ru^III?SalenH₂-Cl₂??PPh₃?Cl]?1?,[Ru^III?SalenH₂-Br₄??PPh₃?Cl]?2?,[Ru^III?SalenH₂??PPh₃?Cl]?3?,[Ru^II?SalanH₂-NH-Cl₂??PPh₃??CO?]?4?and[Ru^II?SalanH₂-NH-Br₄??PPh₃??CO?]?5?in a mixture solvent of ethanol and ether.The molecular structures of complexes 1-5 were confirmed by single-crystal X-ray diffraction,and these complexes were characterized by nuclear magnetic resonance?NMR?,infrared?IR?and ultraviolet?UV?spectroscopies.Additionally,complexes 1-5 were spectroscopically characterized along with investigation of electrochemical properties including electrochemical oxygen evolution and cyclic voltammetry test.