新型氮杂环金属化合物的合成，结构及应用

发布时间：2018-08-15 15:53

【摘要】：本论文中合成并研究了12个新的金属化合物。以苯胺的衍生物Ph N(Li)Si Me_3(L~1)为起始原料,分别与两倍量的二甲基氨基腈或哌啶腈进行加成反应后,再与三分之一量Ti Cl_4(THF)_2反应,培养晶体,最终得到了3个1,3,5-三氮杂戊二烯Ti化合物2a-2c。按照得到化合物2b的实验过程反应后,再与等摩尔量的CH_3Li反应,得到化合物2d-2d'。以2-氨基吡啶的衍生物(2-C_5H_4N)N(H)Si Me_3(L~2)为起始原料,先经等摩尔量的正丁基锂锂化后,再分别与等摩尔量的二甲基氨基腈或哌啶腈进行加成反应后,然后分别与无水Cr Cl_2、Fe Cl_2、Cu Cl_2、Sn Cl_2以不同的比例发生复分解反应,得到了8个1,3,5-三氮杂戊二烯化合物3a-3h。通过X-射线单晶衍射、核磁共振(NMR)、元素分析和熔点测定对这12个化合物进行了详细表征。通过改变反应温度、助催化剂含量等实验条件,对其中两种Ti化合物(2a和2c)对乙烯聚合的催化活性进行研究。具体内容分为三章:第一章,介绍了本论文工作的研究背景、研究意义、研究目的和研究进展。主要内容包括引言、1,3,5-三氮杂戊二烯金属有机化合物、吡啶衍生物类金属有机化合物、金属有机Ti化合物等三个部分。第二章,简述了金属Ti化合物的研究现状。以Ph N(Li)Si Me_3(L~1)为原料,与两倍摩尔量的二甲氨基腈或1-哌啶腈加成后,再与Ti Cl_4(THF)_2发生复分解反应,得到了1,3,5-三氮杂戊二烯Ti化合物2a-2c(Scheme 1)。按照得到2b的实验过程,与Ti Cl_4(THF)_2反应后,再与CH_3Li反应,得到化合物2d-2d'(Scheme 1)。通过X-射线单晶衍射、核磁共振(NMR)、熔点测定和元素分析等手段,对它们的物理和化学性质进行了详细表征。将化合物2a和2c作为主催化剂催化乙烯的聚合反应,通过改变反应温度和Al/Ti对其催化性能进行了具体研究。实验结果为在温度为70℃、Al/Ti为1000时,化合2a的活性达到最大为5.66×10~(4 )g PE·mol~(-1)·h~(-1),化合物2c的催化活性达到最大为4.5×10~(4 )g PE·mol~(-1)·h~(-1)。第三章,简述了吡啶衍生物配体的研究背景和研究现状。以(2-C_5H_4N)N(H)Si Me_3(L~2)为原料,与等摩尔量的正丁基锂反应后,然后与等摩尔量的二甲氨基腈或哌啶腈加成后,再分别与无水Cr Cl_2、Fe Cl_2、Cu Cl_2、Sn Cl_2发生复分解反应,最终得到了8个新的1,3,5-三氮杂戊二烯Cr(II)、Fe(II)、Cu(II)、Sn(II)化合物3a-3h(Scheme 1)。通过X-射线单晶衍射、核磁共振(NMR)、熔点测定和元素分析等手段,对它们的物理和化学性质进行了详细表征。图1化合物2a-2c,和2d-2d'的合成路线Scheme 1 Synthetic routes to complexes 2a-2c,and 2d-2d'Reagents and conditions:i 2Me_2NCN,Et_2O,ca.-78℃;1/3 Ti Cl_4(THF)_2,Et_2O,ca.-78℃.ii 2Me_2NCN,Et_2O,ca.-78℃;1/3 TiCl_4(THF)_2,Et_2O,ca.-78℃.iii 2 1-Piperidinecarbonitrile,Et_2O,ca.-78℃;1/3 TiCl_4(THF)_2,Et_2O,ca.-78℃.iv 2Me_2NCN,Et_2O,ca.-78℃;TiCl_4(THF)_2,Et_2O,ca.-78℃;1/3 CH_3Li,Et_2O,ca.0℃.图2化合物3a-3h的合成路线Scheme 2 Synthetic routes to complexes 3a-3hReagents and conditions:i Bu~(n )Li,Et_2O,0℃;Me_2NCN,Et_2O,ca.-78℃;1/2 Cr Cl_2,Et_2O,ca.-78℃.ii Bu~(n )Li,Et_2O,0℃;1-Piperidinecarbonitrile,Et_2O,ca.-78℃;1/2 Cr Cl_2,Et_2O,ca.-78℃.iii Bu~(n )Li,THF,0℃;Me_2NCN,THF,ca.-78℃;1/2 Fe Cl_2,THF,ca.-78℃;CH_2Cl_2.iv Bu~(n )Li,Et_2O,0℃;Me_2NCN,Et_2O,ca.-78℃;1/2 Cu Cl_2,Et_2O,ca.-78℃.v Bu~(n )Li,Et_2O,0℃;Me_2NCN,Et_2O,ca.-78℃;1/2 Cu Cl_2,Et_2O,ca.-78℃.vi Bu~(n )Li,Et_2O,0℃;1-Piperidinecarbonitrile,Et_2O,ca.-78℃;1/2 Cu Cl_2,Et_2O,ca.-78℃.vii Bu~(n )Li,Et_2O,0℃;Me_2NCN,Et_2O,ca.-78℃;Sn Cl_2,Et_2O,ca.-78℃.
[Abstract]:Twelve new metal compounds were synthesized and studied in this paper. Three 1,3,5-triazapentadiene Ti compounds 2a-1 were synthesized from aniline derivative Ph N(Li)Si Me_3(L~1) by addition reaction with two times of dimethylaminonitrile or piperidinitrile respectively and then with one third of Ti Cl_4(THF)_2. 2c. Compound 2d-2d'. Starting from 2-aminopyridine derivative (2-C_5H_4N) N (H) Si Me_3 (L~2), the compound 2B was lithized with n-butyl lithium and then reacted with dimethylaminonitrile or piperidinitrile respectively. Eight 1,3,5-triazapentadiene compounds 3a-3h were synthesized by double decomposition reaction with anhydrous Cr Cl_2, Fe Cl_2, Cu Cl_2 and Sn Cl_2 in different ratios. The 12 compounds were characterized by X-ray single crystal diffraction, nuclear magnetic resonance (NMR), elemental analysis and melting point determination. The catalytic activities of two Ti compounds (2a and 2c) for ethylene polymerization were studied under different experimental conditions, including the content of Ti, the content of Ti, the content of Ti, the content of Ti, the content of Ti, the content of Ti, the content of Ti, the content of Ti, the content of Ti, the content of Ti, the content of Ti, the content of Ti, the content of Ti, the content of Ti, the content of Ti, the Metallo-organic compounds, organometallic Ti compounds and so on. In the second chapter, the research status of metal Ti compounds is briefly reviewed. The 1,3,5-triazapentadiene Ti compound 2 was synthesized from Ph N (Li) Si Me_3 (L~1) as raw material, which was added with dimethylaminonitrile (DMN) or 1-piperidinitrile (1-piperidinitrile), and then reacted with Ti Cl_4 (THF) _2. A-2c (Scheme 1). According to the experimental process of obtaining 2b, reacting with Ti Cl_4 (THF) _2 and CH_3Li, compounds 2d-2d'(Scheme 1) were obtained. Their physical and chemical properties were characterized by X-ray single crystal diffraction, nuclear magnetic resonance (NMR), melting point determination and elemental analysis. Compounds 2a and 2C were used as main catalysts. The results showed that the activity of 2A reached the maximum of 5.66 (4) g PE (mol) (-1) (-1) (-1) (-1) and compound 2C reached the maximum of 4.5 (4) g PE (mol) (-1) (-1) when the temperature was 70, and Al/Ti was 1000. In this chapter, the research background and present situation of pyridine derivative ligands are briefly described. Eight new compounds are obtained by the reaction of (2-C_5H_4N) N (H) Si Me_3 (L~2) with n-butyl lithium at the same molar amount, then with dimethylaminonitrile or piperidinitrile at the same molar amount, and then with anhydrous Cr Cl_2, Fe Cl_2, Cu Cl_2, Sn Cl_2 respectively. The physical and chemical properties of 1,3,5-triazapentadiene Cr (II), Fe (II), Cu (II), Sn (II) compounds 3a-3h (Scheme 1) were characterized in detail by X-ray single crystal diffraction, nuclear magnetic resonance (NMR), melting point determination and elemental analysis. a-2c,and 2d-2d'Reagents and conditions:i 2Me_2NCN,Et_2O,ca.-78鈩，

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