| Increasing attention has been paid to bis(cyclopentadienyl)metal carbonyl complexes.For the single bridged bis(cyclopentadienyl)metal carbonyl complexes,the structures of bridging groups?the kinds and numbers of substituent group in the cyclopentadienyl have a significant impact on the structures and reactive properties,caused this kind of metal complexes is widely used in organic synthesis reaction.Thus it can be seen,intensive study of these complexes is of great significance,which will not only enrich and develop the metal organic chemistry theory,but also help for the new model of the highly active,so it has potential application prospects.This paper synthesis six single bridged bis(cyclopentadienyl)Mo or Re carbonyl complexes and two aryl bridged bis(tetramethylcyclopentadienyl)Re carbonyl complexes,separation and identification of the structure of aryl bridged bis(tetramethylcyclopentadienyl)Re carbonyl complexes,investigate the influences of Bridging atoms to the structure of the compounds;mainly studied the activity of single bridged bis(cyclopentadienyl)Mo or Re carbonyl complexes and aryl bridged bis(tetramethylcyclopentadienyl)Re carbonyl complexes catalytic Friedel-Crafts acylation reaction,optimized the catalyst system and the reaction conditions,investigated the affection factors of reaction activity,optimized the catalyst system and the reaction conditions,respectively discussed the possible mechanism of single bridged bis(cyclopentadienyl)Mo or Re carbonyl complexes,as well as aryl bridged bis(tetramethylcyclopentadienyl)Re carbonyl complexes catalytic Friedel-Crafts acylation reaction.The main results are listed as following:(1)In this thesis,two single bridged bis(tetramethylcyclopentadienyl)ligands(C5Me4H)E(C5Me4H)[E= p-phenylene(1),p-biphenylene(2)] and three single bridged bis(cyclopentadienyl)ligands(C5H5)E(C5H5)[E= C(CH3)2(5),C(CH2)5(6),Si(CH3)2(7)] were synthesized.Reactions of the five ligands with Re2(CO)10 or Mo(CO)6 in refluxing mesitylene or xylene gave the corresponding two aryl bridged bis(tetramethylcyclopentadienyl)Re carbonyl complexes(E)[(? 5-C5Me4)Re(CO)3]2[E= p-phenylene(3),p-biphenylene(4)]and three dinuclear Re carbonyl complexes(E)[(?5-C5H4)Re(CO)3]2 [E= Si(CH3)2(11),C(C5H10)(12),C(CH3)2(13)] and three dinuclear Mo carbonyl complexes(E)[(?5-C5H4)Mo(CO)3]2 [E= C(CH3)2(8),C(CH2)5(9),Si(CH3)2(10)],The molecular structures of complexes 3,4 were determined by X-ray diffraction analysis.Results show that the Re-Re bond is not formed in the complex 3,4,but the Mo-Mo bond is formed in the complex 8?10.Contrast complexes 3,4 can be found,the kind and structure of bridging atoms influence the length and angel of complexes.(2)The single bridged bis(cyclopentadienyl)Mo carbonyl complexes 8?10catalytic Friedel-Crafts acylation reaction of aromatic compounds with a variety of acylation reagents.The results indicated that: all the molybdenum carbonyl compounds have obvious catalytic activity in Friedel-Crafts acylation reaction.Compared with the traditional catalyst,the Mo carbonyl complexes play the part of Lewis acid in Friedel-Crafts acylation reaction,but the metal carbonyl complexes have obvious advantagesfor example: less dosage,high selectivity,no isomerization reaction,mild reaction condition,simple post-processing and less pollution of the environment so on.(3)When Phenylacetyl chloride and Cyclohexaformyl chloridereacted with aromatic substrates acylation respectively,the conventional product and a small amount of non-target product were obtained;Cinnamoyl chloride with anisole acylation,the conventional product and a small amount of non-target product were obtained;The Benzoyl chloride alone under the action of the catalytic system can react with the organic oxidant o-chloranil directly.By analysis of the non-target product,we designed experiments to further validate the catalytic mechanism.(4)The Rhenium complexes3,4 and 11?13 catalytic Friedel-Crafts acylation reaction of aromatic compounds with a variety of acylation reagents.The results indicated that: all the Rhenium carbonyl compounds have obvious catalytic activity in Friedel-Crafts acylation reaction.Compared with the traditional catalyst,the Re carbonyl complexes play the part of Lewis acid in Friedel-Crafts acylation reaction,but the metal carbonyl complexes have obvious advantagesfor example: less dosage,mild reaction condition,simple post-processing,environmental pollution is small andso on.(5)All unknown complexes were characterized by 1H NMR,13 C NMR,IR spectra,melting point and elemental analysis. |
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