| 中文题名： | 新型二茂铀-端基膦烯化合物的合成、结构及反应性研究 |
| 姓名： | |
| 保密级别： | 公开 |
| 论文语种： | 中文 |
| 学科代码： | 070303 |
| 学科专业： | |
| 学生类型： | 博士 |
| 学位： | 理学博士 |
| 学位类型： | |
| 学位年度： | 2022 |
| 校区： | |
| 学院： | |
| 研究方向： | 金属有机化学 |
| 第一导师姓名： | |
| 第一导师单位： | |
| 提交日期： | 2022-04-07 |
| 答辩日期： | 2022-05-05 |
| 外文题名： | Synthesis, Structure and Reactivity of Novel Terminal Uranium Phosphinidene Metallocenes |
| 中文关键词： | |
| 外文关键词： | organouranium complexes ; actinide ; phosphinidene complexes ; synthesis ; structure ; reactivity |
| 中文摘要： |
研究金属-端基膦烯化合物的合成、性质与反应，开拓其在有机反应中的应用具有重要的学术意义和潜在的应用价值。在过去的30多年中，人们虽然报道了大量的金属-端基膦烯化合物，但主要集中于d-区过渡金属元素，而对其它金属-端基膦烯化合物的研究较少。例如，到目前为止，只有零星几例锕系金属-端基膦烯化合物的结构报道，且对其反应性研究不多。因此，发展新型锕系金属-端基膦烯化合物仍然是个具有挑战性和很有意义的研究工作。本论文以二茂铀甲基氯化物[h5-1,3-(Me3C)2C5H3]2U(Cl)Me (3)和[h5-1,3-(Me3Si)2C5H3]2U(Cl)Me (13)为原料，在Lewis碱Me3PO或Ph3PO存在下，与2,4,6-tBu3C6H2PHK或2,4,6-iPr3C6H2PHK反应，合成出了4例二茂铀-端基膦烯化合物，[h5-1,3-(Me3C)2C5H3]2U(=P-2,4,6-tBu3C6H2)(OPMe3) (4)、[h5-1,3-(Me3C)2C5H3]2U(=P-2,4,6-iPr3C6H2)(OPMe3) (8)、[h5-1,3-(Me3Si)2C5H3]2U(=P-2,4,6-iPr3C6H2)(OPPh3) (15)和[h5-1,3-(Me3Si)2C5H3]2U(=P-2,4,6-iPr3C6H2)(OPMe3) (20)，并对它们的反应性进行了研究。研究发现，二茂铀-端基膦烯化合物在小分子活化方面具有丰富的反应性，例如，化合物15既可作为低价[h5-1,3-(Me3Si)2C5H3]2U(II)合成子与共轭炔烃PhC≡CC≡CPh、偶氮苯PhN=NPh、1,4-二氮杂丁二烯(p-tolylN=CH)2等发生配体的交换(取代)反应，又可与异硫氰酸酯、醛、Schiff碱PhCH=NPh、碳二亚胺、有机腈、炔烃PhC≡CPh、异腈、有机叠氮化物等发生[2+2]、[2+1]或[2+3]环化反应。另外，环戊二烯配体、Lewis碱和膦烯配体的空间位阻和电子效应对二茂铀-端基膦烯化合物的形成和反应性都有重要的影响。此外，反应底物的性质对二茂铀-端基膦烯化合物的反应性也有重要的影响。这些结果揭示了锕系金属-端基膦烯化合物的结构与反应性之间的关系，丰富了锕系金属有机化学，并拓展了对锕系金属有机化合物的认识，为进一步开拓其在有机合成、核工业方面的应用提供了一定的理论基础和实验经验。
﹀
|
| 外文摘要： |
For more than 30 years terminal phosphinidene complexes of d-transition metals have been well-established and they provide very useful entry points to new materials and phosphorus containing (organometallic) molecules, and they are also involved in the construction of phosphorus-element bonds and catalytic applications. Nevertheless, while the chemistry of d-transition metal terminal phosphinidene complexes can now be regarded as a mature field, in which reactivity patterns are well-mapped out and firmly established, only a few derivatives containing actinide metals have emerged so far, and their intrinsic reactivity remained virtually unexplored. Thus, the development of novel actinide compounds with terminal phosphinidene units remains a desirable and challenging goal. In this dissertation, four terminal uranium phosphinidene metallocenes, [h5-1,3-(Me3C)2C5H3]2U(=P-2,4,6-tBu3C6H2)(OPMe3) (4), [h5-1,3-(Me3C)2C5H3]2U(=P-2,4,6-iPr3C6H2)(OPMe3) (8), [h5-1,3-(Me3Si)2C5H3]2U(=P-2,4,6-iPr3C6H2)(OPPh3) (15) and [h5-1,3-(Me3Si)2C5H3]2U(=P-2,4,6-iPr3C6H2)(OPMe3) (20), derived from [h5-1,3-(Me3C)2C5H3]2U(Cl)Me (3), [h5-1,3-(Me3Si)2C5H3]2U(Cl)Me (13), 2,4,6-tBu3C6H2PHK or 2,4,6-iPr3C6H2PHK, in the presence of the Lewis base Me3PO or Ph3PO, have been prepared, and their reactivity has been investigated. The observations show that the terminal uranium phosphinidene metallocenes exhibit a rich reaction chemistry in small molecule activation. For example, compound 15 may act as a masked [h5-1,3-(Me3Si)2C5H3]2U(II) synthon when treated with conjugated alkyne PhC≡CC≡CPh, diazene PhN=NPh and diazabutadiene (p-tolylN=CH)2. Moreover, compound 15 can also ungo [2+2], [2+1] or [2+3] cycloaddition reactions with internal alkynes and various hetero-unsaturated molecules such as imines, carbodiimides, isothiocyanates, aldehydes, nitriles, isonitriles and organic azides. Moreover, the steric and electronic effects of the cyclopentadienyl ligands, Lewis base ligands and phosphinidene ligands have large effect on the formation and reactivity of the terminal uranium phosphinidene metallocenes. Furthermore, the properties of the substrates also modulate the reactivity of the terminal uranium phosphinidene metallocenes. These results demonstrate the structure-reactivity relationship of the organoactinide complexes, which help us understand the reactivity of the actinides, thus narrow the knowledge gap between the transition metals and the actinides. In addition, these results would provide insights into their potential for organic synthesis and nuclear engineering, which is not only of academic but also industrial interests.
﹀
|
| 参考文献总数： | 193 |
| 作者简介： | 王士春，北京师范大学有机化学博士，研究方向为金属有机化学，期间主要从事金属铀-端基膦烯化合物的合成、结构及反应性研究，在研究过程中发现环戊二烯配体、Lewis碱和膦烯配体的空间位阻和电子效应对二茂铀-端基膦烯化合物的形成和反应性都有重要的影响。以第一作者身份在《Inorganic Chemistry》，《Organometallics》，《Dalton Transactions》等期刊上发表5篇。 |
| 馆藏地： | 图书馆学位论文阅览区（主馆南区三层BC区） |
| 馆藏号： | 博070303/22005 |
| 开放日期： | 2023-06-07 |
谷歌
