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）-（+）-α-methylbenzylamine（LNO*11）and N-（2-hydroxy-5-chloro-benzylidene）-（R）-（+）-2-amino-3-phenyl-1-propanol（LNO*10）resultedinformationofaacyl-rutheniumcomplex[Ru（η²-C,O-salBr₂）Cl（NO）（PPh₃）₂]and a cationic complex[Ru（η²-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.