| Increasing attention has been paid to the progress on the study of bis(cyclopentadienyl) metal carbonyl complexes. The single bridged bis(cyclopentadienyl) metal carbonyl complexes is one of the most important bis(cyclopentadienyl) metal carbonyl complexes. For the single bridged bis(cyclopentadienyl) metal carbonyl complexes, the structure 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, separation and identification of the structure of single bridged bis(cyclopentadienyl) 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 catalytic Friedel-Crafts alkylation 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 catalytic Friedel-Crafts alkylation reaction. The main results are listed as following:(1) In this thesis, three single bridged bis(cyclopentadienyl) ligands(C5H5)R(C5H5) [R = C(CH3)2(1), C(CH2)5(2), Si(CH3)2(3)] were synthesized.Reactions of the three ligands with Re2(CO)10 or Mo(CO)6 in refluxing mesitylene or xylene gave the corresponding three dinuclear Re carbonyl complexes[(η5-C5H4)R(η5-C5H4)]Re2(CO)6 [R = C(CH3)2(4), C(C5H10)(5), Si(CH3)2(6)] and three dinuclear Mo carbonyl complexes [(η5-C5H4)R(η5-C5H4)]Mo2(CO)6 [R =C(CH3)2(7), C(CH2)5(8), Si(CH3)2(9)], The molecular structures of complexes 5, 6were determined by X-ray diffraction analysis. Results show that the Re-Re bond is not formed in the complex 4~6, but the Mo-Mo bond is formed in the complex 7~9.Contrast complexes 4~9 can be found, the kind and structure of bridging atoms not only influence the length and angel of complexes, but also influence the dihedral angle and torsion angle of man-ring.(2) The Rhenium complexes 4~6 catalytic Friedel-Crafts alkylation reaction of benzene derivative with a variety of alkylation reagents were studied, respectively.The results indicated that all the Re carbonyl complexes catalytic Friedel-Crafts alkylation reaction show different activity due to the difference of benzene derivatives and alkylating reagent. The same as the traditional catalyst, the Re carbonyl complexes play the part of Lewis acid in Friedel-Crafts alkylation reaction, but the metal carbonyl complexes have obvious advantages, for example: less dosage, mild reaction condition, simple post-processing, environmental pollution is small, close to the advantages of green chemistry and so on.(3) The Molybdenum complexes 7~9 catalytic Friedel-Crafts alkylation reaction of benzene derivative with a variety of alkylation reagents were studied, respectively.The results indicated that all the Re carbonyl complexes catalytic Friedel-Crafts alkylation reaction show different activity due to the difference of benzene derivatives and alkylating reagent. The same as the traditional catalyst, the Mo/o-chloranil carbonyl complexes play the part of Lewis acid in Friedel-Crafts alkylation reaction.but the metal carbonyl complexes have obvious advantages, for example: less dosage,recyclabl, emild reaction condition, simple post-processing, environmental pollution is small, close to the advantages of green chemistry and so on.(4) All unknown complexes were characterized by 1H NMR, 13 C NMR, IR spectra, melting point and elemental analysis... |
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