Syntheses, Reactions And Application Of Fused Cyclopentadienyl Metal Complexes

This thesis covers mainly three aspects. (1) Reactions of methyl-substituted indene and dihydro-s-indacene derivatives with Ru3(CO)12. (2) Reactions of (diphenylphosphino)indene derivatives with benzyne. (3) Synthesis of benzyl tricarbonyl molybdenum complexes of methyl-substituted indene and dihydro-s-indacene derivatives and their application in radical polymerization.(1) A series of methyl-substituted indene and dihydro-s-indacene ligands were synthesized [C9H6Me2 (1), C9H3Me5 (2), C9H5Me3 (3), C12H2Meg (4) and C12H4Me6 (5)]. Thermal treatment of 4 with Ru3(CO)12 afforded complexes Ru3(η5:η5:η2-C20H24)(CO)7 (6) and Ru4(η5:η4:η1-C20H24)(μ-CO)2(CO)7(7), via intramolecular sp3 C-H bond activation, and the mononuclear complex Ru(η5-C20H25)(CO)2Cl (8). Reaction of 1 and 2 with Ru3(CO)12 also yielded the tetranuclear complex Ru4(η5:η3:η2-C14H16)(CO)9 (9) via the same sp3 C-H bond activation, together with the dinuclear complex [(η5-C9H2Me5)Ru(CO)]2(μ-CO)2 (10) and [(η5-C9H5Me2)Ru(CO)]2(μ-CO)2 (11). Reaction of 5 with Fe(CO)5 gave a dinuclear complex [(η5:η3-C9H3Me5)Fe(CO)5] (12). However, There was no product in the reaction of 3 and 5 with Ru3(CO)12 and the reactions of 1-4 with Fe(CO)5 owing to the poor reactivity.(2) A series of substituted (diphenylphosphino)indene derivatives were synthesized, their reactions with benzyne were explored. Different types of (diphenylphosphino)indene derivatives reacted with benzene to produce different products due to the steric and electronic effects of substitutents. Some substrates reacted with benzyne gave the phosphinium triflates through ring expansion. Other (diphenylphosphino)indene derivatives converted to the Wittig Reagents.(3) A series of benzyl tricarbonyl molybdenum complexes of methyl-substituted indene and dihydro-s-indacene derivatives were synthesized, and applied in radical polymerization of MMA and Styrene. Some characteristics of living radical polymerization were found. The substituents had great effects on the reactivity of polymerization, while there was no evident relationship between the reactivity and steric and electronic effects of substituents.