【作者】 王梅；

【导师】 姚英明；

【作者基本信息】 苏州大学 ， 有机化学， 2004， 硕士

【摘要】 本论文采用胍基为含氮辅助配体，合成了8个钛有机配合物，并对其中3个配合物进行了X-光结构鉴定，考察配合物中各原子间的成键方式。在此基础上，进一步研究了这些配合物对苯乙烯的催化聚合活性。合成2个胍基锂盐，对其中一个配合物进行了X-光结构测定，考察各原子间的成键方式。尝试2，4-Bu^t₂-1-OH-C₆H₂-C=N-（4‘-R-1’-OH-C₆H₄）（R=Bu^t，H）为含氮辅助配体，合成2个[ONO]钛有机配合物。 1．二异丙胺基锂盐与1倍量Cy=C=Cy（二环己基二亚胺）发生插入反应，得到配合物1。2，6-二异丙基苯胺基锂盐分别与1倍量Cy=C=Cy发生插入反应，得到配合物2。配合物经过了红外光谱，核磁，元素分析，其中配合物1经过X-光结构的表征。 2．胍基锂盐[Pr₂ⁱNC（NCy）₂]Li，[Ph₂NC（NCy）₂]Li，[Ph₂NC（NPrⁱ）₂]Li，[(C₅H₁₀)NC（NCy）₂]Li，[(C₅H₁₀)NC（NPrⁱ）₂]Li，（Cy=cyclohexyl，Prⁱ=isopropyl，Ph=phenyl）与TiCl₄（THF）₂按2：1的摩尔比发生反应，以中等产率得到深红色固体[Pr₂ⁱYC（NR）₂]₂TiCl₂[（R=Cy）（3）]，[Ph₂NC（NR）₂]2TiCl₂[R=Cy（4）；R=Prⁱ（5）]，[(C₅H₁₀)NC（NR）₂]₂TiCl₂[R=Cy（6）；R=Prⁱ（7）]。这些配合物经过了红外光谱，核磁，元素分析，其中配合物3，7经过X-光结构的表征。 3．二异丙基胺锂与配合物3以2：1的摩尔比发生反应，以THF为溶剂，得到THF的开环产物[Pr₂ⁱNC（NCy）₂]₂Ti（OCH₂CH₂CH₂CH₃）₂（8）。这个配合物经过了红外光谱，核磁，元素分析和X-光结构的表征。 4．配合物2与TiCl₄（THF）₂按2：1的摩尔比发生反应，得到不对称胍基钛配合物（9）。这个配合物经过了红外光谱，核磁，元素分析的表征。 5．环戊二烯钠与TiCl₄（THF）₂按1：1的摩尔比发生反应，产物与胍基锂盐[Pr₂ⁱNC（NCy）₂]Li按1：1的摩尔比发生反应，得到单茂单胍钛配合物[Pr₂ⁱNC（NCy）+2]CpTiCl₂（10）。这个配合物经过了红外光谱，核磁，元素分析的表征。 6．以2，4-Bu^t₂-1-OH-C₆H₂-C=N-（4’-R-1’-OH-C₆H₄）（R=Bu^t，H）为辅助配体，合成配合物[ONO]钛有机配合物11，12。 8．配合物[Pr₂ⁱNC（NR）₂]₂TiCl₂[（R=Cy）（3）]，[Ph₂NC（NR）₂]₂TiCl₂[R=Cy（4）；R=Prⁱ版墓钦配合物的制备、表征及俄化性能的研究中文摘致合物IONOj钦有机配合物11，12。 8.配合物[prZ’NC困R)2]ZTICI:l（R=Cy）（3）l，[PhZNC困R)2]ZTICI:[R=Cy（4）:R=Pr，（5）]，[（C。H，。）NC（NR）2〕ZTICI:[R=Cy（6）;R=pr，（7）]等配合物与改性的甲基铝氧烷（MMAO）组成催化体系，可以催化苯乙烯的聚合，其催化活性中等。初步研究结果还显示这一催化体系得到的聚苯乙烯主要是间同聚合物。更多还原

【Abstract】 Seven guanidinate titanium complexes were first synthesized and well characterized. Three complexes of them were characterized by X-ray diffraction structural analysis. The catalytic behaviors of some guanidinate titanium complex were tested.1. Reaction of Pr’N=C=NPri with lithium diisopropylamide in THF afforded the guanidinate lithium (i-PrN)C[NPr’2](N/-Pr)}Li}2(THF)2 (1).2. CyN=C=NCy reacted with lithium 2,6-diisopropylaniline in 1:1 molar ratio to produce the asymmetric guanidinate lithium [Cy(H)NC(NCy)(NC6H5-2,6-Pr’)Li(THF)]2 (2).3. Guanidinate lithium [Pr2iNC(NCy)2]Li, [Ph2NC(NCy)2]Li, [Ph2NCCNPr]Li, [(C5H10)NC(NCy)2]Li, [(C5H10)NC(NPri)2]Li, (Cy = cyclohexyl, Prj = isopropyl, Ph = phenyl) formed in situ reacted with TiCl4(THF)2 in 2:1 molar ratio to produce the guanidinate titanium chloride [Pr2iNC(NR)2]2TiCl2 [(R = Cy) (3)], [Ph2NC(NR)2]2TiCl2 [R = Cy (4); R = Prj (6)], [(C5Hi0)NC(NR)2]2TiCl2 [R = Cy (6);R = Prj (7)] in good yield. Their structure was characterized by elemental analyses, !H NMR, IR. Complexes 3 and 7 were characterized by X-ray crystal structure determination.4. Reaction of [Pr2iNC(NCy)2]2TiCl2 with lithium diisopropylamide in THF afforded the unexpected [Pr2’NC(NCy)2]Ti(OBun)2 (8), which was formed by the cleavage of the carbon-oxygen bond of THF. Complex 8 was characterized by elemental analysis, *H NMR. IR, and X-ray crystal structure determination.5. Guanidinate lithium 2 formed in situ reacted with TiCl4(THF)2 in 1:1 molar ratio to produce complex [Cy(H)NC(NCy)(NC6H5-2,6-Pr1)]2TiCl2 (9). Complex 9 was characterized by elemental analysis, ’H NMR, IR.6. CpNa (Cp = C5Hs) reacted with TiCl4(THF)2 in 1:1 molar ratio to produce the cyclopentadienyl titanium chloride CpTiChfTHF), then reacted with guanidinate lithium[Pr2’NC(NCy)2]Li(Cy = cyclohexyl) formed in situ in 1:1 molar ratio to produce the cyclopentadienyl-guanidinate titanium chloride [Pr2’NC(NR)2]CpTiCl2 (10). Complex 10 was characterized by elemental analyses, ’H NMR, IR.7. [2,4-BuVl-OH-C6H2-C=N-(4’-R-r-OH-C6H4)] (R = Bu1 , H ) [ONO] reacted with n-BuLi in 1:1 molar ratio to produce lithium salt, and then reacted with TiCl4(THF)2 in 1:1 molar ratio to produce [ONO]TiCl2(R = Bu111, R = H 12).8. The catalytic activities of complexes 3-7 in the presence of MMAO for the styrene polymerization were tested. The preliminary results indicated that the polystyrenes obtained are syndiotactic polymers.更多还原