Organo-ruthenium Complexes Bearing Phosphine Ligands With Functionalized Organic-Si（OR）₃ Groups

A series of organometallic ruthenium complexes containing phosphine and amine ligands were synthesized,especially,immobilization of organo-ruthenium complexes bearing phosphine ligands with functionalized organic-Si（OR）₃ groups on nano-silicon oxide resulted in formation of immobilized heterogeneous catalyses was investigated in this thesis.Three phosphine ligands containing organosilane moieties[Ph₂PN（CH₂）₃Si（OCH₃）₃]（L1）,[N,N’-（PPh₂）₂N（CH₂）₃Si（OCH₃）₃]（L2）and[Ph₂PS-（CH₂）₃Si（OEt）₃]（L3）,and two tridentate phosphine/amine-containing Schiff base ligands[2-（C₅H₄N）CH=N（CH₂）₂N（CH₃）₂]（L4）,[Ph₂P（o-C₆H₄）CH=N（CH₂）₂N-（CH₃）₂]（L5）were synthesized in detail,for examples,ligands L1 and L2 were obtained from reaction ofγ-aminopropyltrimethoxysilane and chlorodiphenylphos-phine in molar ratios of 1:1 and 1:2,repectively;ligand L3 was isolated from reaction solution ofγ-mercaptopropyltrimethoxysilane and chlorodiphenylphosphine in molar ratio of 1:1 in refluxing toluene;ligands L4 and L5 were harvested from the reaction of 2-pyridinecarboxaldehyde or 2-diphenylphosphinobenzaldehyde and 2-dimethyla-minoethylamine in molar ratio of 1:1 in refluxing toluene,respectively.Ligands L1-L5 were well characterized by nuclear magnetic resonance（NMR）and infrared（IR）spectroscopies.Treatment of organoruthenium startings[（η⁶-p-cymene）RuCl₂]₂and[（η⁶-C₆H₆）RuCl₂]₂ with different phosphine ligands resulted in isolation of series of organo-ruthenium complexes with the according phosphine ligands,[（η⁶-p-cymene）RuCl₂（κ¹-P-L1）]（1）,[（η⁶-C₆H₆）RuCl₂（κ¹-P-L1）]（2）,[（η⁶-p-cymene）-Ru（μ₂-Cl）₃RuCl（κ²-P,P-L2）]（4）and[（η⁶-C₆H₆）RuCl（κ²-P,P-L2）]（5）.However,complexes[Ru（bpy）₂Cl（κ¹-P-PPh₂OCH₃）]（3）and[（η⁶-p-cymene）RuCl₂（κ¹-P-Ph₂OH）]（6）were sometimes formed inevitably due to cleavage of P-N bond and hydrolysis of original phosphine ligands.Treatment of different ruthenium startings[RuCl₂（PPh₃）₃],cis-[Ru（DMSO）₄Cl₂],[Ru（cod）Cl₂]₂,[Ru（NO）Cl₃?xH₂O],[RuHCl（CO）（PPh₃）₃]or[Ru（CO）₂Cl₂]_n with phosphine/amine-containing Schiff base ligands afforded series of mononuclear ruthenium complexes with the according ligands,[Ru（PPh₃）₂Cl₂（κ²-N,N-L6）]（7）,[Ru（DMSO）₂Cl₂（κ²-N,N-L6）]（8）,[Ru（COD）Cl（κ²-N,N-L6）]（9）,[Ru（CO）₂-Cl₂（κ²-N,N-L6）]（10）,[Ru（PPh₃）Cl₂（κ³-N,N,N-L4）]（11）,[Ru（CO）Cl₂（κ³-N,N,N-L4）]（12）,[Ru（PPh₃）（CO）Cl（κ³-N,N,N-L4）]（13）,[Ru（NO）Cl₂-（κ³-N,N,N-L4）]（14）,[Ru（CO）Cl₂（κ³-P,N,N-L5）]（15）and[Ru（NO）Cl₂（κ³-P,N,N-L5）]（16）.Complexes1-16 were spectroscopically characterized along with investigation of electrochemical properties including electrochemical hydrogen evolution of complexes 2 and 4,of which molecular structures of complexes 2,3,4,6,7·Et₂O,11 and 15 were unambiguously established by single-crystal X-ray diffraction.Additionally,complexes 2 and 4 contianing phosphine ligands with functionalized organic-Si（OR）₃groups were immobilized on SBA-15 by way of an immersion method,leading to formation of the corresponding heterogeneous catalysts 2/SBA-15 and 4/SBA-15.The immobilized heterogeneous catalysts 2/SBA-15 and 4/SBA-15 were analysized by the infrared spectroscopy,transmission electron microscope（TEM）and brunauer emmett teller（BET）.Hydrogenation of acetophenone catalyzed by the immobilized heterogeneous catalysts was also investigated.