Synthesis And Catalytic Property Of Ruthenium Complexes With Pyridyl Ligands

The study of ruthenium complexes is an important research field of organometallic chemistry in which ruthenium complexes with pyridyl ligands are research hotspots in recent years.Benefited from varied coordination modes,many kinds of suitable reaction and good catalytic effect,the ruthenium complexes with pyridyl ligands are widely used in catalysis and have got rich research product ion.In this dissertation,a series of ligands with pyridyl were designed and synthesized and treated with precursor ruthenium complexes to get corresponding ruthenium products.These complexes were used for catalytic reactions ofβ-alkylation of secondary alcohols with primary alcohols and benzyl alcohol oxidizing to benzoic acid.The main contents of this dissertation include the following three parts:（1）Two pyridyl indenes（1 and 3）and one pyridyl cyclopentadiene（8）were synthesized.Twoprecursorrutheniumcomplexes,Ru Cl₂（PPh₃）₃and Ru HCl（CO）（PPh₃）₃,were synthesized.Five ruthenium complexes（13,14,15,16 and 17）with pyridyl ligands were obtained from the reactions of the ligands with precursor ruthenium complexes.The design features of these ruthenium products were discussed and analyzed.（2）The catalytic experiment about theβ-alkylation of secondary alcohols with primary alcohols was investigated by the catalysis of these synthesized ruthenium complexes.The reaction conditions were optimized on the basis of complex 14 as the best catalyst and expanded the substrates of this reaction.Taking complexes 14 as an example,the possible catalytic mechanism ofβ-alkylation of secondary alcohols with primary alcohols was analyzed and deduced.（3）The catalytic experiment about the reaction of benzyl alcohol oxidizing to benzoic acid was also investigated.Optimal catalytic condition was identified by using complex 14 as the catalyst and expanded the substrates of this reaction,whose possible catalytic mechanism was analyzed and deduced.In this dissertation,five unknown compounds and five known compounds were synthesized.The known compounds except complex 16 were characterized by ¹H NMR,³¹P NMR and IR spectroscopy.Three organometallic complexes were characterized by X-ray single crystal diffraction to confirm their crystal structures.