Synthesis And Characterization Of Ruthenium Carbene/Phosphine/Sulfur Complexes Supported By Multidentate Cyclic Amine Ligands

Transition metal complexes bearing multi-dentate cyclic amine ligands are widely used in biochemistry and chemical catalysis due to their special stability.Two cyclic amine compounds of 1,4,7-trimethyl-l,4,7-triazacyclononane（Me₃tacn）and 1,4,7,10-tetraazacyclododecane（cyclen）are employed to react with Ru Cl₃·H₂O to give corresponding complexes（Me₃tacn）Ru Cl₃·H₂O and[（cyclen）Ru（dmso）Cl]Cl（dmso=dimethylsulfoxide）.Then,the two ruthenium complexes are studied in detail and the main work are carried out currently:（1）Reaction of（Me₃tacn）Ru Cl₃·H₂O with substituted bipyridine in the presence of zinc powder afforded[（Me₃tacn）Ru（R-bpy）（H₂O）]（PF₆）₂（bpy=2,2’-bipyridine）compounds with a labile aqua ligand.Interaction of[（Me₃tacn）Ru（R-bpy）（H₂O）]（PF₆）₂and 1,1-diphenylpropargyl alcohol afforded ruthenium（II）methoxycarbene complexes[（Me₃tacn）（R-bpy）Ru=C（OMe）CH=CPh₂]（PF₆）₂（R=H,1;4,4’-Me₂,3;5,5’-Me₂,5;4,4’-di-^tBu,7）in methanol;similar reaction in tetrahydrofuran afforded ruthenium（II）allenylidene complexes[（Me₃tacn）（R-bpy）Ru=C=C=CPh₂]（PF₆）₂（R=H,2;4,4’-Me₂,4;5,5’-Me₂,6;4,4’-di-^tBu,8）.Complexes 1-8 were well characterized by infrared,UV/Vis,mass spectrometry,and NMR spectroscopies.The crystal structures of complexes 3,5,and 6 have been established by single-crystal X-ray diffractometer.The transformation of ruthenium（II）allenylidene complexes to ruthenium（II）methoxycarbene complexes are also studied.（2）（Me₃tacn）Ru Cl₃·H₂O reacted with dithiolate ligands.（a）Reactions using ROCS₂Na afforded disulfide-bridged dinuclear ruthenium（II/III）complexes[（Me₃tacn Ru）₂（η-S₂COR）（η-S₂CO）（μ-S₂）]PF₆（R=Me,9;Et,10;Pr,11;ⁱPr,12）;Reactionsusingdialkyldithiophosphates（RO）₂PS₂Kafforded[（Me₃tacn）Ru（S₂P（OR）₂）Cl]PF₆（R=Me,13;Et,14;Pr,15;ⁱPr,16）.All complexes were well characterized by infrared and UV/Vis spectroscopies.The crystal structures of complexes 10 and 12 have been determined by single-crystal X-ray diffractometer.The properties of photocatalytic water splitting of complexes 9-12 were also investigated.（3）Interaction of[（cyclen）Ru（dmso）Cl]Cl with dialkyldithiocarbamate ligands R₂NCS₂Na and dithiocarbamate ligands ROCS₂Na gave complexes[（cyclen）Ru（S₂CNR₂）]PF₆（R=Me,17;Et,18;ⁿPr,19;ⁱPr,20）and[（cyclen）Ru（S₂COR）]PF₆（R=Et,21;ⁿPr,22;ⁱPr,23）,respectively.All complexes were characterized by infrared and UV/Vis spectroscopies.（4）After removing coordinated chlorine atom of（Me₃tacn）Ru Cl₃·H₂O by silver nitrile,further reaction with dppe/dppp（dppe=Ph₂P（CH₂）₂PPh₂;dppp=Ph₂P（CH₂）₃PPh₂）ligands produced[（Me₃tacn）Ru（dppe）Cl]PF₆（24）and[（Me₃tacn）Ru（dppp）Cl]PF₆（25）respectively.The infrared and UV/Vis properties were also investigated for these complexes.The crystal structure of complex 24 has been also established by single-crystal X-ray diffractometer.