| In this work, the addition reactions of arylamine to nitriles (two types of a-hydrogen-free nitrile:Me2NCN,2-PyCN) were studied. PhN(Li)SiMe3(L1), (Dipp)N(Li)SiMe3 (L2, Dipp=2,6-’Pr2-C6H3) were used as starting materials to react with 2-cyanopyridine or dimethylcyanamide and gave an a-diketinimate-lithium salt and a 1,3,5-triazapentadienate lithium salt. The appropriate lithium compounds reacted with metal halides form the corresponding metal complexes. Nine novel complexes were obtained and their structures were characterized by various analysis methods such as NMR, elemental analysis and single crystal X-ray diffraction. The thesis included the following four chapters.Chapter 1. The introduction part involves the background of this research and divided into three sections:(1) introduction of organometallic chemistry; (2) the synthesis and related applications of amidinate metal complexes; (3) the synthesis and related applications of 1,3,5-triazapentadienate metal complexes.Chapter 2. The reaction of PhN(Li)SiMe3L1) with a-hydrogen-free 2-cyanopyridine and TMEDA at the ratio of 1:1 led to complex 2a (Scheme 1). Complex 2a was characterized by NMR (1H NMR, 13C NMR,7Li NMR), EA and single crystal X-ray diffraction.Scheme 1 Synthesis of complex 2aReagents and conditions:i 2-PyCN, TMEDA, Et2O, ca.-78℃.Chapter 3. The reactions of PhN(Li)SiMe3(L1) or (Dipp)N(Li)SiMe3(L2) to dimethylcyanamide at ratio of 1:2 or 1:3 and then with CuX (X=Cl, Br, I) led to seven Cu (I), Cu (II) complexes 3a-3g (Scheme 2 and Scheme 3). Complexes 3a-3g were characterized by NMR (1H NMR,13C NMR), EA and single crystal X-ray diffraction. The structures were compared with their analogues.Scheme 2 Synthesis of complexes 3a-3eReagents and conditions:i 2Me2NCN, CuX (X=C1, Br, I), Et2O, ca.-78℃; ii 2Me2NCN, CuBr, Et2O, ca.-78℃; ⅲ 2Me2NCN, CuBr, Et2O, ca.-78 ℃; ⅳ 2Me2NCN, CuBr, Et2O, ca.-78℃; ⅴ 3Me2NCN, CuBr, Et2O, ca.-78℃. Reagents and congditions:ⅵ 2Me2NCN, CuCl2, Et2O, ca.-78℃; ⅶ 2Me2NCN, 1/2CuCl2, Et2O, ca.-78℃.Chapter 4. The reactions of PhN(Li)SiMe3(L1) to dimethylcyanamide at ratio of 1:2 and then with AICl3 1ed to an A1 complex 4a (Scheme 4). Complex 4a was characterized by single crystal X-ray diffraction and elemental analysis. |
