Syntheses And Structures Of Asymmetric Ruthenium Complexes Supported By N,O,S-Tridentate Ligands

Transition metal ruthenium complexes have been widely applied in the fields of electrochemical,catalytic,bio-organometallic and solid-state chemistry.Synthetic reaction,structural characterization and applied properties of asymmetric ruthenium complexes containing N,O,S-tridentate ligands were well investigated in this thesis.Three tridentate mono-anionic ligands of the N,O,S-donor sites Schiff-bases,namely 3,5-di-bromo-N-（2-（methylsulfanyl）phenyl）salicylaldimine（HL1）,5-chloro-N-（2-（methylsulfanyl）phenyl）salicylaldimine（HL2）,and 3,5-di-tert-butyl-N-（2-（methylsulfanyl）phenyl）salicylaldimine（HL3）were pepared by condensation reaction.Reaction of[Ru（PPh₃）₃Cl₂]with equal equiv.of HL1 in tetrahydrofuran solution in the presence of triethylamine afforded complex[Ru（L1）（PPh₃）₂Cl]（1）with two triphenylphosphine ligands trans to each other.Treatment of HL2 with one equiv.of[Ru HCl（CO）（PPh₃）₃],[Ru（CO）₂Cl₂]_n or cis-[Ru Cl₂（DMSO）₄]（DMSO=dimethylsulfoxide）gave complexes[Ru（L2）（CO）（PPh₃）Cl]（2）,[Ru（L2）（CO）₂Cl]（3）,and[Ru（L2）（DMSO）₂Cl]（4）,respectively.Interactions between HL3 and[Ru（CO）₂Cl₂]_n,[Ru（COD）Cl₂]₂（COD=1,5-cyclooctadiene）,or Ru Cl₃·3H₂O resulted in isolation of ruthenium（II）complexes[Ru（L3）（CO）₂Cl]（5）,[Ru（L3）（COD）Cl]（6）,and[Ru（L3）₂]（7）,respectively.Complexes 1～7 were characterized by microanalyses,FT-IR and NMR spectroscopies,and the structures of all complexes have been unambiguously established by single-crystal X-ray crystallography.The electrochemical properties of complexes 1～7 were also investigated.Treatment of[（η⁶-C₆H₆）Ru Cl₂]₂ or[（η⁶-p-cymene）Ru Cl₂]₂ with two equiv.of L-methionine in the presence of Ag NO₃ and Na OMe gave mononuclear ruthenium（II）complexes[（η⁶-C₆H₆）Ru（L-met）]（NO₃）（8）and[（η⁶-cymene）Ru（L-met）]（NO₃）（9）,respectively.Interactions between equal equiv.of L-methionine and[Ru（CO）₂Cl₂]_n,[Ru（bpy）₂Cl₂]·2H₂O（bpy=2,2?-bipyridine）,[Ru（NO）（PPh₃）₂Cl₃],（Et₄N）[Ru（CH₃CN）₂Cl₄]or cis-[Ru（DMSO）₄Cl₂]resulted in isolation of the expected ruthenium complexes[（CO）₂Ru（L-met）Cl]（10）,[（bpy）₂Ru（L-met）]Cl（11）,[Ru（L-met）（NO）（PPh₃）Cl]Cl（12）,[Ru（L-met）（CH₃CN）Cl₂]（13）and[Ru（L-met）（DMSO）₂Cl]（14）,respectively.In addition,reaction of[Ru（COD）Cl₂]₂with L-methionine gave a dinuclear ruthenium complex[（COD）Ru（μ-S-L-met）（μ-Cl）Ru Cl（L-met NMe₂）]（15）and a mononuclear ruthenium complex[（COD）Ru（L-met）Cl]（16）.Complexes 8～16 were characterized by microanalyses,FT-IR,NMR and UV-vis spectroscopies.The structures of complexes 8,9,11,15and 16 have been unambiguously established by single-crystal X-ray crystallography.The photocatalytic properties for hydrogen production by water oxidation of complexes 8,9,11 and 15 under visible light（λ>420 nm）were also investigated.