| 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 of?-aminopropyltrimethoxysilane and chlorodiphenylphos-phine in molar ratios of 1:1 and 1:2,repectively;ligand L3 was isolated from reaction solution of?-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[??6-p-cymene?RuCl2]2and[??6-C6H6?RuCl2]2 with different phosphine ligands resulted in isolation of series of organo-ruthenium complexes with the according phosphine ligands,[??6-p-cymene?RuCl2??1-P-L1?]?1?,[??6-C6H6?RuCl2??1-P-L1?]?2?,[??6-p-cymene?-Ru??2-Cl?3RuCl??2-P,P-L2?]?4?and[??6-C6H6?RuCl??2-P,P-L2?]?5?.However,complexes[Ru?bpy?2Cl??1-P-PPh2OCH3?]?3?and[??6-p-cymene?RuCl2??1-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??2-N,N-L6?]?7?,[Ru?DMSO?2Cl2??2-N,N-L6?]?8?,[Ru?COD?Cl??2-N,N-L6?]?9?,[Ru?CO?2-Cl2??2-N,N-L6?]?10?,[Ru?PPh3?Cl2??3-N,N,N-L4?]?11?,[Ru?CO?Cl2??3-N,N,N-L4?]?12?,[Ru?PPh3??CO?Cl??3-N,N,N-L4?]?13?,[Ru?NO?Cl2-??3-N,N,N-L4?]?14?,[Ru?CO?Cl2??3-P,N,N-L5?]?15?and[Ru?NO?Cl2??3-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. |
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