Synthesis And Characterization Of Ruthenium Complexes With Immobilizable Organosilicone Groups

Transition metal ruthenium complexes have broad application prospects in homogeneous and heterogeneous catalytic hydrogenation, catalytic oxidation and catalytic hydrodesulfurization?HDS?. This thesis mainly discusses the synthesis,crystal structure and catalytic properties of ruthenium complexes containing organosilicone ligands.Treatment of N1-?3-?trimethoxysilyl?propyl?ethane-1,2-diamine?L₁? with one equiv. of [Ru?PPh₃?₃Cl₂], [Ru?DMSO?₄Cl₂], [Ru?COD?Cl₂]n, [Ru?CO?₂Cl₂]n or[Ru?THT?₄Cl₂] in refluxing tetrahydrofuran?THF? or toluene gave complexes[Ru?PPh₃?₂Cl₂??²-N-L₁?] × CH₂Cl₂?1?, [Ru?DMSO?₂Cl₂??²-N-L₁?]?2?, [Ru??4-C8H12?-Cl₂??²-N-L₁?]?3?, [Ru?CO?₂Cl₂??²-N-L₁?]?4? and [Ru?THT?2Cl₂??²-N-L₁?]?5?,respectively. The crystal structures of 1 × CH₂Cl₂, 2, and 3 have been obtained by single-crystal X-ray diffraction, and these complexes 1-5 have also been characterized by the infrared and 31P{1H} NMR spectroscopies. Complexes 1 and 3have been immobilized on SBA-15 by an immersion method. 1/SBA-15 and3/SBA-15 have been characterized by the infrared, thermogravimetric analysis,transmission electron microscope?TEM? and sorption studies?BET?, and applied in catalytic oxidation of benzyl alcohol to benzaldehyde. Their yields were 4.75% and5.47%, respectively.Interaction of salicylaldehyde, 5-chlorosalicylaldehyde or pyridine-2-carboxaldehyde with one equiv. of ?-aminopropyltriethoxysilane in refluxing ethanol afforded organosilicone ligands HL₂, HL₃ and L₄, respectively. Treatment of dimeric[Ru??6-p-cymene? Cl?m-Cl?]2with two equiv. of Ag NO3, followed by two equiv. of organosilicone ligands HL₂ and HL₃ in the presence of triethylamine in acetonitrile and THF afforded [Ru? ? 6-p-cymene?Cl??-N,?-O-L₂?]?6? and[Ru? ? 6-p-cymene?Cl??-N,?- O-L₃?]?10?, respectively. Reactions of [Ru?NO?Cl₃],[Ru?C₅Me₅?Cl₂]2 or [Cp Ru?PPh3?Cl₂] with one equiv. of organosilicone ligands HL₂ or HL₃ in the presence of triethylamine in refluxing THF afforded[Ru?NO?Cl₂?Et2O???-N,?-O-L₂?]?7?, [Ru?C₅Me₅?Cl??-N,?-O-L₂?]?8?,[Cp Ru?PPh3???-N,?-O-L₂?]?9?, [Cp Ru?PPh3?-??-N,?-O-L₃?]?12? and[Ru?C₅Me₅?Cl??-N,?-O-L₃?]?13?, respectively. Reactions of [Ru?PPh₃?₃Cl₂] with two equiv. of organosilicone ligands HL₃ in the presence of triethylamine in refluxing THF afforded [Ru?PPh3?Cl??-N,?-O-L₃?2]?11?. Treatment of organosilicone ligands L₄ and ?-methacryloxy propyl trimethoxyl silane?L₅? with [Ru?PPh₃?₃Cl₂], [Ru?CO?₂Cl₂]n,[Ru?DMSO?₄Cl₂] or [Ru?NO?Cl₃] in refluxing THF afforded [Ru Cl₂?PPh3?2??²-N-L₄?]?14?, [Ru?CO?₂Cl₂??²-N-L₄?]?15?, [Ru?DMSO?₂Cl₂??²-N-L₄?]?16?,[Ru?NO?Cl₃??²-N-L₄?]?17? and [Ru?PPh₃?₂Cl₂??-MAA?]?18?, respectively. The crystal structures of 6, 7, 10, 11 and 18 have been obtained by single-crystal X-ray diffraction, and these complexes 6-18 have also been characterized by the infrared and 31P{1H} NMR spectroscopies. Complexes 7, 10 and 11 have been immobilized on SBA-15 by an immersion method. 7/SBA-15, 10/SBA-15 and 11/SBA-15 have been characterized by the infrared, thermogravimetric analysis, transmission electron microscope?TEM? and sorption studies?BET?, and studied in catalytic oxidation of benzyl alcohol to benzaldehyde. Their yields were 6.81%, 12.67% and 2.51%,respectively.Reactions of ?-aminopropyltriethoxysilane with one equiv. of KPPh2 in THF afforded organosilicone phosphine ligand L₆. Reactions of ?-aminopropyltriethoxysilane with two equiv. of chlorodiphenylphosphine in the presence of triethylamine in toluene afforded organosilicone phosphine ligand L₇. Reactions of?-aminopropyltriethoxysilane with 2-?diphenylphosphino?benzaldehyde in refluxing ethanol afforded organosilicone phosphine ligand L₈. Interaction of dimeric [Ru? ? 6-p-cymene?Ru? m-Cl?Cl]2? [Ru? ? 6-C₆H₆?Cl₂]2 or [Ru?C₅Me₅?Cl₂]2 with L₆ in refluxing THF afforded [Ru??6-p-cymene?Cl₂??-P-L₆?]?19?, [Ru??6-C₆H₆?Cl₂??-P-L₆?]?20?, and [Ru?C₅Me₅?Cl₂? ?-P-L₆?]?21?, respectively. Reactions of [Ru?CO?₂Cl₂]n,[Ru?PPh₃?₃Cl₂] or [Ru?DMSO?₄Cl₂] with L₇ in refluxing THF afforded[Ru?CO?₂Cl₂??²-P-L₇?]?22?, [Ru?PPh₃?₂Cl₂??²-P-L₇?]?23?, and[Ru?DMSO?₂Cl₂??²-P-L₇?]?24?, respectively. Reactions of [Ru?THT?₄Cl₂],[Ru?DMSO?₄Cl₂], [Ru?PPh₃?₃Cl₂] or [Ru?CO?₂Cl₂]n with L₈ in refluxing THF afforded[Ru?THT?₂Cl₂??-P,?-N-L₈?]?25?, [Ru?DMSO?₂Cl₂??-P,?-N-L₈?]?26?,[Ru?PPh₃?₂Cl₂??-P,?-N-L₈?]?27? and [Ru?CO?₂Cl₂??-P,?-N-L₈?]?28?, respectively.The crystal structure of 19 has been obtained by single-crystal X-ray diffraction, and these complexes 19-28 have also been characterized by the infrared and 31P{1H}NMR spectroscopies.