锰（钴）卟啉卡宾化合物的合成与性质研究

发布时间：2018-07-08 16:33

本文选题：卟啉 + 卡宾　；参考：《山西师范大学》2017年硕士论文

【摘要】：以氮杂环卡宾为配体的过渡金属配合物由于具有独特的催化功能而成为非常重要的研究对象,受到了化学界的广泛关注和深入研究。这些氮杂环卡宾作为配体,其特殊之处体现在与配位中心金属产生的配位键不同于依靠具有孤对电子的杂原子或者π键体系等传统配体,故而具有多种特殊的结构与化学性质。在以往的研究中,常见的与氮杂环卡宾配位的金属有:Ru、Rh、Ir及Pd,而对第三周期金属的研究和报道相对较少,尤其是针对氮杂卡宾与Co和Mn的配合物的研究更是寥寥。本研究通过N-杂环卡宾与金属卟啉的配位反应制备了一系列五配位卡宾-锰(钴)卟啉的配合物,并分离得到了单晶样品。通过紫外可见吸收光谱与电子顺磁共振光谱等手段对这些化合物进行了表征和研究。本课题使用TPP(四苯基卟啉)、TTP(四甲基苯基卟啉)等卟啉,设计、合成并分离了三个以氮杂环卡宾(1,3-Me2Imd)为轴向配体的锰卟啉模型化合物:[M n(T P P)(1,3-M e 2 I m d)](C c)、[M n(T P P)(1,3-M e2I m d)](P 2 1/n)、[Mn(T TP)(1,3-M e2 Imd)],并进行了X-ray单晶衍射表征;其单晶结构及EPR谱图与其它类似的五配位锰卟啉(咪唑衍生物和氰基衍生物)的对比表明这些配合物具有五配位高自旋二价锰卟啉的典型特征。同时也使用了含有吸电子基团的TFPP(5,10,15,20-四(五氟苯基)卟啉)卟啉,设计合成了以二苯基碳卡宾为配体的锰卟啉模型化合物,并对产物进行了电子顺磁共振谱(EPR)以及紫外可见光谱(UV-vis)的表征。我们使用TPP卟啉,设计合成了[Co(TPP)(1,3-Me2Imd)],并分离出了晶体,通过与五配位钴卟啉咪唑衍生物作对比,使我们对氮杂环卡宾配位的钴卟啉有了更进一步的了解。通过对卡宾-金属卟啉化合物的单晶结构、紫外可见吸收光谱和电子谱学的研究,加深了人们对卡宾配位场的理解,为卡宾与金属卟啉的深入研究乃至应用于催化反应奠定了一定基础。
[Abstract]:The transition metal complexes with heterocyclic carbenes as ligands have become an important research object due to their unique catalytic function. As ligands, these nitrogen heterocyclic carbenes are characterized by their special structure and chemical properties, which are different from those of traditional ligands such as heteratoms with solitary electrons or 蟺 bond systems. In the past studies, the common coordination metals with nitrogen heterocyclic carbene are: Ru-rh RhIr and PD, but the third cycle metal is less studied and reported, especially for the complexes of nitrogen heterocyclic carbene with Co and mn. A series of five-coordinated carben-manganese (cobalt) porphyrin complexes were prepared by the coordination reaction of N-heterocyclic carbene with metalloporphyrin, and the single crystal samples were isolated. These compounds were characterized and studied by UV-vis absorption spectra and electron paramagnetic resonance spectroscopy. The design of TPP (tetraphenylporphyrin) TTP (tetramethylphenyl porphyrin) isoporphyrin was used in this paper. Three manganese porphyrin model compounds, [M _ n (T P) (1H _ 3-M e _ 2i m d)] (C c), [M _ n (T P) (1n (T P) (1n) Me _ 2i m d)], [mn (T _ (TP) (n ~ (3) Me _ 2Imd)], [mn (T _ (TP) (n ~ (3) Me _ (2Imd)]), were synthesized and separated. The comparison of the single crystal structure and EPR spectra with other similar five-coordination manganese porphyrins (imidazole derivatives and cyanyl derivatives) shows that these complexes have the typical characteristics of five-coordination high-spin divalent manganese porphyrins. At the same time, the manganese porphyrin model compound with diphenyl carbamate as ligand was designed and synthesized by using TFPP (5H10ON1520- Tetrafluorophenyl) porphyrin containing electron absorbent group. The products were characterized by electron paramagnetic resonance (EPR) and UV-vis spectra. Using TPP porphyrin, we have designed and synthesized [Co (TPP) (1HP-3-Me2Imd)] and isolated the crystal. By comparing with the penta-coordinated Cobalt-porphyrin imidazole derivative, we have gained a better understanding of the Cobalt porphyrin coordinated by heterocyclic carbene. The study of the single crystal structure, UV-Vis absorption spectrum and electron spectroscopy of carben-metalloporphyrin compounds has deepened the understanding of carbene coordination field. It lays a foundation for the further study of carbens and metalloporphyrins and their application in catalytic reactions.
【学位授予单位】：山西师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.1

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