| The thesis mainly focused on the synthesis and catalytic reactivity of titanium and zirconium complexes incorporating imidazole ligands. It's composed of following three parts.Firstly, four imidazole ligands, L1, L2, L3 and L4, (L1 = 4, 5-diphenyl- 2-(2-pyri -dinyl)-1H-imidazole, L2 = 4, 5-bis(4-chlorophenyl)-2-(2-pyridinyl)-1H-Imidazole, L3 = 4, 5-bis(4-methoxyphenyl)-2-(2-pyridinyl)-1H-imidazole, and L4 = 4, 5-bis(2-meth- -oxyphenyl)-2-(2-pyridinyl)-1H-imidazole), were designed and fourteen novel titanium and zirconium complexes of formula Ti(L1)(NMe2)3 (1), Ti(L2)(NMe2)3 (2), Ti(L3)(NMe2)3 (3), Ti(L4)(NMe2)3·THF (4), Zr(L1)(NMe2)3 (5), Zr(L2)(NMe2)3·THF (6), Zr(L3)(NMe2)3 (7), Ti(L1)2(NMe2)2·THF (8), Ti(L2)2(NMe2)2·THF (9), Ti(L3)2(NMe2)2·THF (10), Ti(L4)2(NMe2)2 (11), Zr(L1)2(NMe2)2·1.5THF (12), Zr(L2)2(NMe2)2·0.5THF (13), and Zr(L3)2(NMe2)2·0.5THF (14) were synthesized. The crystal structures of 2 and 9 were determined by X-ray diffraction, NMR spectroscopy and elemental analysis. The other complexes were characterized by NMR spectroscopy and elemental analysis.Secondly, the hydroamination reactions of alkynes catalyzed by 2 and 9 were investigated. It is noteworthy that complexes 2 and 9 have been very efficient catalysts for regioselective Markovnikov hydroamination of 1-octyne. In addition, the reaction occurs with high regioselectivity (100:0) and preferring the Markovnikov products.Thirdly, four kinds of aminoalkenes and one aminoalkyne were synthesized. To evaluate the catalytic ability of zirconium complexes, the intramolecular hydroamination of the aminoalkenes and aminoalkyne catalyzed by complexes 6 and 13 have been investigated. |
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