| 题名 | 新型磺酰脒铑(II)配合物的合成及其在催化氧化反应中的应用 |
| 作者 | 阿不都热合曼 乌斯曼 |
| 学位类别 | 博士 |
| 答辩日期 | 2012-05-26 |
| 授予单位 | 中国科学院研究生院 |
| 授予地点 | 北京 |
| 导师 | 卢崇道 |
| 关键词 | 磺酰脒铑(II)配合物 设计与合成 催化 氧化活泼C–H键 过氧叔丁醇 |
| 学位专业 | 有机化学 |
| 中文摘要 | 发展新型双核铑(II)配合物，并研究这些配合物作为催化剂在有机化学反应中的应用，是金属有机化学领域的重要研究方向之一。目前，N,N-配位的双核铑(II)配合物作为催化剂的应用还未见报道，设计与合成该类型的铑(II)配合物并研究其催化活性是富有挑战性的研究工作。本论文围绕这一主题开展相关研究。 首先，我们合成了一小类具有环状结构的磺酰脒类化合物，通过这些化合物与醋酸铑进行配体交换反应得到了三种新型N,N-配位磺酰脒铑(II)配合物，Rh2(Msip)4， Rh2(Tsip)4和Rh2(PMPsip)4。同时研究了配体的制备到配合物的合成过程中每一步反应的特性以及反应条件对收率的影响。通过单晶X-射线衍射分析确定该类配合物为（3, 1）异构体；循环伏安扫描实验结果显示这三种配合物的第一氧化电位分别为570mV，546mV和542mV (vs. Ag/AgCl)；紫外可见光谱实验结果表明：这些配合物在叔丁基过氧化氢(TBHP)的作用下，会被氧化，在紫外可见光谱低能量区域出现新的特征吸收峰。 进一步研究表明：磺酰脒铑(II)配合物Rh2(Msip)4可以作为催化剂，催化含有苄位碳氢键的化合物的氧化反应。以TBHP作为氧化剂，在温和反应条件下，该催化剂可以顺利地将各种含有苄位碳氢键的底物氧化成相应的羰基化合物。研究结果显示，反应溶剂对反应的影响较大，水作为溶剂时，该氧化反应的效率比无水条件下高得多。 此外，研究过程中还发现：非常低催化量(0.1mol%)的Rh2(Msip)4对苄醇等含有活泼C–H键的醇类化合物显示出很高的催化活性，把各种结构的苄醇，烯丙醇和炔丙醇氧化成相应的酮或酸(醛)，同时不影响分子内的脂肪醇官能团，可以达到选择性氧化的目的。 到目前为止，本论文开发的新型磺酰脒铑(II)配合物，是目前唯一可以用于催化有机化学转化的电中性N,N-配位的铑(II)配合物。该研究对N,N-配位的铑(II)配合物的深入研究和发展，具有重要意义。 |
| 英文摘要 | Development of new dirhodium (II) complexes and evaluating their potentials as a catalyst in organic transformations are one of the pursuit goals in the field of organometallic chemistry. Up to now the studies on the applications of N, N-ligated dirhodium (II) complexes as a catalyst in chemical transformations are rare. Therefore, design and synthesis of new dirhodium (II) sulfonylamidinates and exploration of their catalytic activities are challenging. This paper focused on this subject and the related investigations were conducted. Firstly, we synthesized a small class of cyclic sulfonylamidines, with which ligand exchange reactions of dirhodium(II)acetate were carried out to generate three new N, N-ligated dirhodium sulfonylamidinate complexes, which are Rh2(Msip)4 , Rh2(Tsip)4 and Rh2(PMPsip)4. The preparation of ligands and complexes was investigated and the detailed reaction conditions for these processes were evaluated. The structures of above three compounds have been established through single crystal X-ray diffraction, which indicated that these complexes adopt (3, 1)- geometric configuration. Their cyclic voltammogram have been characterized and the first one-electron oxidation potentials were 570 mV, 546 mV and 542 mV (vs. Ag/AgCl), respectively. The UV-visible spectrum of the complexes upon addition of t-BuOOH revealed a characteristic low energy adsorption. After that, Rh2(Msip)4 was employed to test its capacity in catalytic benzylic oxidation in conjunction with stoichiometric amount of tert-butyl hydrogen peroxide (TBHP) as oxidant. The reaction proceeds well under mild conditions and a range of benzylic substrates were oxidized to the corresponding carbonyl compounds with good yields. Investigations showed that the solvent effect on the reaction is quite significant and the catalytic activity of Rh2(Msip)4 in water is much higher than that in anhydrous condition. Further studies indicated that Rh2(Msip)4 is active in catalytic oxidation of the activated alcohols with a very low catalytic loading(0.1 mol%). Various benzylic, allylic and propargylic alcohols were oxidized to corresponding ketone or acid(aldehyde) under mild reaction conditions while other intramolecular hydroxyl groups was unaffected.. Thus, selective oxidation can be achieved by this protocol. To date, the complexes described herein serve as the only effective neutral N,N-ligated dirhodium(II) complexes to catalyze organic transformations. This will have an important impact on further exploration in this field. |
| 内容类型 | 学位论文 |
| 源URL | [http://ir.xjipc.cas.cn/handle/365002/4405]  |
| 专题 | 新疆理化技术研究所_资源化学研究室 |
| 作者单位 | 中国科学院新疆理化技术研究所 |
| 推荐引用方式 GB/T 7714 | 阿不都热合曼 乌斯曼. 新型磺酰脒铑(II)配合物的合成及其在催化氧化反应中的应用[D]. 北京. 中国科学院研究生院. 2012. |
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