Synthesis Of [（η⁵-C₅Me₄R）Mo（CO）₃]I And Their Catalytic Application In Friedle-Crafts Alkylation

Increasing attention has been paid to metallocene carbonyl complexes, especially the dinuclear metallocene complexes, due to the significant cooperative effect of both metal centers on their reactivity and catalytic applications. While, for the mononuclear halogenated metallocene carbonyl complex, because of the existence of halogen element makes it better to activate the metal atoms, improve reaction and catalyst activity. Intensive study of these complexes is of great significance, which will not only enrich and develop the metal organic chemistry theory, also help for the new model of the highly active and selective catalyst. This paper studies the reactivity of dual-core substituted tetramethylcyclopentadienyl molybdenum carbonyl compounds with I2, separation and identification of the structure of substituted tetramethylcyclopentadienyl molybdenum carbonyl iodides, investigate the influences of mau-ring substituent to the structure of the compounds, especially to Mo-I bond distance, mainly studied the activity of dual-core molybdenum carbonyl compounds and mononuclear tetramethylcyclopentadienyl molybdenum carbonyl iodides 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 dual-core molybdenum carbonyl compounds and mononuclear molybdenum carbonyl iodines catalytic Friedel- Crafts alkylation reaction. The main results are listed as following:(1) In this thesis, 5 substituted tetramethylcyclopentadienyl ligands [(C5Me4H)R] [R= allyl(1), nBu(2), tBu(3), Ph(4), Pz(5)] were synthesized. Reactions of the five ligands with Mo(CO)3(Me CN)3 in refluxing xylene gave the corresponding five dinuclear metal carbonyl complexes [(η5-C5Me4R)Mo(CO)3]2 [R= allyl(6), nBu(7), tBu(8), Ph(9), Bz(10)].(2) Research the reactivity of the five dinuclear metal carbonyl complexes with I2, in chloroform solution, and obtained five kinds of mononuclear substituted tetramethylcyclopentadienyl molybdenum carbonyl iodines [(η5-C5Me4R)Mo(CO)3]I [R= allyl(11), nBu(12), tBu(13), Ph(14), Bz(15)]. The molecular structures of complexes 12, 13 and 15 were determined by X-ray diffraction analysis. Results show that the substituent in the mau-ring can directly affect Mo-I bond distances of the complexes, the greater the space steric hindrance of substituent, lead to Mo-I bond length increase.(3) Respectively studied the compounds 6 ~ 15 catalytic Friedel- Crafts alkylation reaction of aromatic compounds with a variety of alkylation reagents. The results indicated that: all the molybdenum carbonyl compounds have obvious catalytic activity in Friedel- Crafts alkylation reaction. Relatively, the mononuclear compounds showed higher catalytic activity. Compared with the traditional catalysts, the metal carbonyl complexes have obvious advantages, for example: less dosage, mild reaction condition, high selectivity, no isomerization reaction, 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.