【作者】 姚海生；

【导师】 沈琪；

【作者基本信息】 苏州大学 ， 有机化学， 2007， 硕士

【摘要】 以芳氧基功能化的氮杂环卡宾前体为辅助配体，合成并表征了芳氧基功能化的氮杂环卡宾稀土胺化物，卡宾断裂的芳氧稀土配合物以及离子对结构的咪唑盐稀土钕配合物，主要结果如下：1将LiNⁱPr₂和SmCl₃按照4：1的摩尔比在THF／己烷混合液中反应，首次合成并单晶结构鉴定了配合物Li（THF）Sm（NⁱPr₂）₄（1）。2将芳氧基功能化的氮杂环卡宾前体[HO-4，6-di_<sup>tBu-C₆H₂-2-CH₂{CH（NCHCH N） ⁱPr}] Cl（A）、Li（THF）Ln（NⁱPr₂）₄（Ln=Y，Nd，Sm）和n-BuLi按照摩尔比2∶1∶1，在-78℃反应，成功地得到了三例芳氧基功能化的氮杂环卡宾稀土胺化物：[O-4，6-di-^tBu-C₆H₂-2-CH₂-{C（NCHCHNⁱPr）}]₂LnNⁱPr₂（Ln=Y（2），Nd（3），Sm（4）），产物都经过了元素分析，红外，及单晶结构等分析表征，配合物2也经过了¹HNMR，¹³CNMR的表征。3初步研究了配合物2，3，4对己内酯，丙交酯的催化聚合活性，发现他们都可以催化己内酯，丙交酯的聚合，聚合物的分子量分布较宽；并尝试了配合物4和小分子PhNCO的插入反应。4将NaOAr、SmCl₃和[HO-4，6-di-^tBu-C₆H₂-2-CH₂{CH（NCHCHN）Me}]Cl（B）以4∶1∶1摩尔比，采用一锅煮的方法，希望得到芳氧基功能化的氮杂环卡宾稀土芳氧配合物没有取得成功，而是得到了断裂的产物[O-4，6-di-^tBu-C₆H₂-2-[CH{N（CHCH）NMe}]][（O-4，6-di-^tBu-C₆H₂）₂CH₂][O-2，4-di-^tBu-C₆H₃][N（CH（MeN）CHCH）]Sm（THF）（5）。配合物5经过了元素分析，红外及X—单晶结构的分析表征。5将A、NdCl₃按照2∶1的摩尔比，常温下，在THF中搅拌，反应，经处理，得到了离子对结构的配合物[NdCl₅（THF）]^2- [HO-4，6-di-^tBu-C₆H₂ 2-CH₂{CH（ⁱPrNCHCHN）}]₂⁺ （6），6经红外，元素分析，X—单晶结构表征。尝试了配合物6和碱（NaN（SiMe₃）₂，LiNⁱPr₂）的反应，希望能用此方法得到氮杂环卡宾稀土卤化物或其衍生物。更多还原

【Abstract】 We synthesized and characterized lanthanides amide complexes of （Y, Nd, Sm） supported by aryloxo-functional N-heterocyclic carbene, an bridged bisphenoxide complexe of lanthanide from the cleavage of aryloxo-functional N-heterocyclic carbenes and an ion-pairs complex supported by aryloxo-functional N-heterocyclic carbene precursor. The main results as fellows:1. The amide complex of samarium Li（THF）Sm（NⁱPr₂）₄ （1） was synthesized and characterized by the reaction of LiNⁱPr₂ with SmCl₃ in 4:1 molar ratio in THF and hexane,2 Reaction of aryloxo-functional N-heterocyclic carbene precursor [HO-4, 6-di-^tBu-C₆H₂-2-CH₂{CH（NCHCHN）ⁱPr}]Cl （A） , Li（THF）Ln（NⁱPr₂）₄ （Ln= Y, Nd, Sm） and n-BuLi in 2:1:1 molar ratio in THF at -78℃for 10h, and at room temperature for 12h, gave the corresponding complexes [0-4, 6-di-^tBu-C₆H₂-2-CH₂-{C（NCHCHNⁱPr）}]₂ LnNⁱPr₂ （Ln=Y（2）, Nd（3）, Sm（4））. All complexes were fully characterized by IR, elemental analysis, X-ray diffraction, and by ¹HNMR and ¹³CNMR in the case of Y.3. The catalytic activity of complexes 2, 3 and 4 for e-Caprolactone and L-lactide polymerization were examined. All the complexes can catalyse polymerization of e-Caprolactone and L-lactide, gave the polymers with rather broader molecular weight distribution.4. Reaction of NaOAr, SmCl₃ and aryloxo-functional N-heterocyclic carbene precursor [HO-4, 6-di-^tBu-C₆H₂-2-CH₂{CH（NCHCHN）Me}]Cl （B） in 4:1:1 molar ratio in THF in one-pot hadn’t afforded an anionic phenoxide complex of samarium （5） supported by a bridged bisphenoxo through the cleavage of aryloxo-functional N-heterocyclic carbenes. The complexes 5 was characterized by IR, elemental analysis, X-ray diffraction.5 Reaction of aryloxo-functional N-heterocyclic carbene precursor A with NdCl₃ in 2:1 molar ratio in THF yielded an ion-pairs complex 6, The complex 6 was characterized by IR, elemental analysis, and X-ray diffraction. The further reaction of 6 with alkali （NaN（SiMe₃）₂, LiNⁱpr₂） were tried and no definite complexes were isolated.更多还原