本文選題：卟啉 + 卡賓�。� 參考：《山西師范大學(xué)》2017年碩士論文

【摘要】：以氮雜環(huán)卡賓為配體的過(guò)渡金屬配合物由于具有獨(dú)特的催化功能而成為非常重要的研究對(duì)象,受到了化學(xué)界的廣泛關(guān)注和深入研究。這些氮雜環(huán)卡賓作為配體,其特殊之處體現(xiàn)在與配位中心金屬產(chǎn)生的配位鍵不同于依靠具有孤對(duì)電子的雜原子或者π鍵體系等傳統(tǒng)配體,故而具有多種特殊的結(jié)構(gòu)與化學(xué)性質(zhì)。在以往的研究中,常見的與氮雜環(huán)卡賓配位的金屬有:Ru、Rh、Ir及Pd,而對(duì)第三周期金屬的研究和報(bào)道相對(duì)較少,尤其是針對(duì)氮雜卡賓與Co和Mn的配合物的研究更是寥寥。本研究通過(guò)N-雜環(huán)卡賓與金屬卟啉的配位反應(yīng)制備了一系列五配位卡賓-錳(鈷)卟啉的配合物,并分離得到了單晶樣品。通過(guò)紫外可見吸收光譜與電子順磁共振光譜等手段對(duì)這些化合物進(jìn)行了表征和研究。本課題使用TPP(四苯基卟啉)、TTP(四甲基苯基卟啉)等卟啉,設(shè)計(jì)、合成并分離了三個(gè)以氮雜環(huán)卡賓(1,3-Me2Imd)為軸向配體的錳卟啉模型化合物:[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)],并進(jìn)行了X-ray單晶衍射表征;其單晶結(jié)構(gòu)及EPR譜圖與其它類似的五配位錳卟啉(咪唑衍生物和氰基衍生物)的對(duì)比表明這些配合物具有五配位高自旋二價(jià)錳卟啉的典型特征。同時(shí)也使用了含有吸電子基團(tuán)的TFPP(5,10,15,20-四(五氟苯基)卟啉)卟啉,設(shè)計(jì)合成了以二苯基碳卡賓為配體的錳卟啉模型化合物,并對(duì)產(chǎn)物進(jìn)行了電子順磁共振譜(EPR)以及紫外可見光譜(UV-vis)的表征。我們使用TPP卟啉,設(shè)計(jì)合成了[Co(TPP)(1,3-Me2Imd)],并分離出了晶體,通過(guò)與五配位鈷卟啉咪唑衍生物作對(duì)比,使我們對(duì)氮雜環(huán)卡賓配位的鈷卟啉有了更進(jìn)一步的了解。通過(guò)對(duì)卡賓-金屬卟啉化合物的單晶結(jié)構(gòu)、紫外可見吸收光譜和電子譜學(xué)的研究,加深了人們對(duì)卡賓配位場(chǎng)的理解,為卡賓與金屬卟啉的深入研究乃至應(yīng)用于催化反應(yīng)奠定了一定基礎(chǔ)。
[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.
【學(xué)位授予單位】：山西師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O641.1

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