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Synthesis, characterization and activity of 2-methylimidazole side-chain functionalized Group 4 metallocenesдипломная работа (Специалист)
- Научный руководитель: Borzov Maxim V.
- Автор: Xu Yingying
- Тип: Специалист
- Организация, в которой проходила защита: College of Chemistry and Material Science, the North-West University of Xi’an, Taibai Bei Avenue 229, Xi’an 710069, Shaanxi Province, People’s Republic of China
- Год защиты: 2012
- Аннотация: In recent years, the so-called Constrained Geometry complexes (CGCs) for olefin polymerization are the objects in the focus of the studies in the modern organometallic chemistry. On the other hand, the Frustrated Lewis pairs (FLPs) are also becoming very popular and attract a great deal of attention due to their recently discovered capability to activate small molecules. The present research mainly focuses on the synthesis of a particular C2-bridged cyclopentadienyl-amido type CGCs and studies of its reactivity towards electrophilic reagents SiMe3Cl and Lewis acid AlBn3, B(C6F5)3. In addition, attempts of activation of C02 by FLPs based on the complex were undertaken. The preparation route for C5H5-CPh2CH2-(imidazol-2-yl) ligand 2b was improved that increased both the yield and the purity. The target Cp-tris(amido) type complexes, 2-[2-(h5-cyclopentadienyl)-2-methylpropyl]-1H-imidazolyl-bis(N,N-diethylamido)titanium(iv)(3a) and 2-[2-(h5-cyclopentadienyl)-2,2-diphenylethyl]-lH-imidazolyl-bis(N,N-diethylamido) titanium (iv) (3c) have been synthesized. Reactions of the amido-complex 3c with electrophilic reagents, trimethylchlorosilane and thribenzylaluminum, has afforded trichloro-2-[2-(h5-cyclopentadienyl)-2,2- diphenylethyl]-1-trimethylsilyl-1H-imidazolyl-titanium(iv) (Sa) and 2-[2-(h5-yclopentadienyl)-2,2-diphenylethyl]-1-[tris(phenylmethyl)aluminiumyl]-1H-imidazole-bis(N,N-diethylamido)titanium(iv)(6b). Compounds 3a, 3c, Sa, have been synthesized and characterized by 1HNMR, 13CNMR spectroscopy and X-ray diffraction analysis, and 6b has been synthesized and characterized by X-ray diffraction analysis. B(C6F5) 3 as a strong Lewis acid can react with amine complexes 3c in order to get an FLP capable to activate C02 . The symmetry of the structure of the 3c-B(C6F5)3 reaction product is lower than that of 3c. Unfortunately, we failed to gain single crystals of this compound suitable for the X-ray diffraction analysis.
- Добавил в систему: Борзов Максим Владимирович
Прикрепленные файлы
| № | Имя | Описание | Имя файла | Размер | Добавлен |
|---|---|---|---|---|---|
| 1. | Полный текст | Xu_Yingying.pdf | 22,7 МБ | 26 ноября 2018 [BorzovMV] |