Synthetic Reactions And Molecular Structures Of Ruthenium Complexes Supported By The Me₃tacn Tripod Ligands

1,4,7-Trimethyl-l,4,7-triazacyclononane Me₃tacn is a chemically stable cyclic amine,which has been widely used as a ligand that affects bioinorganic chemistry and catalysis.In this thesis,starting from the divalent ruthenium compound[（Me₃tacn）Ru（DMSO）Cl₂]（1）,which was refluxed in concentrated hydrochloric acid in air to obtain the ruthenium（III）complex[（Me₃tacn）Ru Cl₃·H₂O]（2）in high yield.Treatment of complex 2 with bipyridine,thiocarbamate,and carboxylateled to isolation of a series of mono-and binuclear ruthenium（II/III）complexes.The work of this thesis is mainly as follows.In the presence of zinc powder as a reducing agent,reactions of[（Me₃tacn）Ru Cl₃·H₂O]（2）with bipyridine-type compounds in refluxing water gave the ruthenium（II）complexes[（Me₃Tacn）Ru（R-bpy）（H₂O）]（Cl O₄）₂（R=H,3;4,4’-Me₂,4;5,5’-Me₂5;4,4’-ⁿBu₂,6）,respectively.The labile hydrate ligand in ruthenium（II）compounds containing bipyridine unit could easily be replaced by pyridine,acetonitrileandcarbeneligndtoaffordcomplexes[（Me₃Tacn）Ru（5,5’-Me₂bpy）（CH₃CN）]²⁺（7）,[（Me₃Tacn）Ru（bpy）（Py）]²⁺（8）,[（Me₃Tacn）Ru（5,5’-Me₂bpy）（Py）]²⁺（9）and[（Me₃Tacn）（bpy）Ru=C（OMe）CH₂Ph]²⁺（10）.The ruthenium complexes 3～9 were characterized by UV-Vis,FT-IR,and NMR spectroscopies,and the structures of complexes 1,1·4H₂O,4,7,8,9 and 10 have been determined by single-crystal X-ray diffraction.The photocatalytic properties for hydrogen production by water hydrolysis of complexes 3,5 and 6 were also investigated.Reactions of[（Me₃tacn）Ru Cl₃·H₂O]（2）with DTC and carboxylate ligands led to isolationofthecorrespondingruthenium（III）complexes[（Me₃tacn）Ru（S₂CNR₂）Cl]（PF₆）（R=Me,11;Et,12;ⁱPr,13;ⁿPr,14;ⁿBu,15）and dinuclear ruthenium（III）complexes[（Me₃tacn）₂Ru₂（μ-O）（μ-O₂CR）₂]（PF₆）₂(R=Ph,16;Py,17;C₆H₄-2-Cl,18;C₆H₃-2,4-Cl₂,19;CH₂C₆H₄-2-CH₃,20;CH₂C₆H₄-4-CH_3,21;CH₂C₆H₄-4-OCH_3,22;CH₂C₆H₄-4-Cl,23).The isolated ruthenium（III）complexes were characterized by FT-IR、fluorescence and UV-Vis spectrocopies,and the structures of complexes 12～14,16,17,20,22 and 23 were determined by single-crystal X-ray diffraction.The electrochemical properties of several complexes were also investigated.The photocatalytic properties for hydrogen evolution by water hydrolysis of complexes 16,17,18,20 and 22 were also investigated.