Synthesis,Reactivity And Catalytic Property Of Ruthenium Complexes With Indenyl And Pyridyl Ligands

C-C coupling is the core of organic chemistry.C-C bond activation via C-H bond activation has the advantages of atomic economy and high synthesis efficiency.However,the intermediates with M-C and M-H bonds in these reactions are always instable,which restricts to understand the mechanisms.If we could explore the reactivity of some organometallic complexes with similar structures as these intermediates,it will be helpful for understanding the mechanisms.In this dissertation,a series of indenyl pyridyl ligands were designed and synthesized.These ligands reacted with ruthenium complexes,and a series of complexes with Ru-C bonds were obtained via C-H bond activation.The reactivity and catalytic property of these ruthenium products were explored.The main contents of this dissertation include the following two parts.?1?6-methyl-1-?2-pyridyl?indene?2?was synthesized from 6-methyl-1-indano-ne.2 could further react with Ru₃?CO?₁₂ to form triruthenium complex {?₂-?¹:?⁵-?C₅H₄N?(C₁₀H₇)Ru₃?CO?₉?3?.And the reactivity of compound 3 with a series of olefins or alkynes was then studied.The corresponding ruthenium products were formed via the insertion of olefins or alkynes into Ru-C??¹?bond of 3.The reaction mechanisms were discussed and the results are significant for understanding the Ru-catalyzed C-H/olefin or alkyne coupling reactions.?2?1-?2-pyridyl?indene?11?was synthesized from 1-indanone as starting materials.Compounds 2,11 and indene were then reacted with Ru Cl2?PPh3?3 to form novel indenyl pyridine ruthenium complexes {?C₅H₄N?(?⁵-C₁₀H₇)?C₆H₄PPh₂?}RuCl?PPh₃??12?,{?C₅H₄N???⁵-C₉H₅??C₆H₄PPh₂?}RuCl?PPh₃??13?and {??⁵-C₉H₇?PPh₃)₂Cl?14?with ?⁵ coordination mode,respectively.The possible mechanisms for the formation of compound 12 and 13 were proposed.In addition,the catalytic experiment about the isomerization of allyl alcohol was investigated with compound 12 and 13 as catalysts and the reaction conditions were optimized for the reaction,whose possible catalytic mechanism was analyzed and deduced.In this dissertation,nine unknown compounds and six known compounds were synthesized.The compounds were characterized by ¹H NMR,¹³C NMR,IR spectroscopy and elemental analysis.Four organometallic compounds were characterized by X-ray single crystal diffraction to confirm their crystal structures.