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采用密度泛函理论B3LYP方法研究了咔咯锰(Ⅴ)氧配合物(MnⅤO corrole)与苯乙烯氧原子转移(oxygen atom transfer,OAT)反应途径和吸电子取代基的影响。计算结果发现氧原子进攻苯乙烯中双键的β碳原子形成过渡态,结合内禀反应坐标法(intrinsic reaction coordinate method,IRC)和最小能量交叉点(minimum-energy crossing point,MECP)计算,给出该反应发生直接氧转移的机理。咔咯大环中位连的吸电子五氟苯基可通过改变锰原子的亲电性,加大取代基与氧原子的静电排斥作用,增加MnⅤO corrole的氧化性。反应能垒随五氟苯基数目的增加而降低,且三重态的反应能垒明显低于单重态。体系可从单重态反应物开始,在MECP处易发生自旋翻转并形成三重态,然后以能量更低的三重态过渡态反应路径进行氧转移反应直至生成产物。 相似文献
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以五氟苯甲醛和吡咯经缩合反应合成了五氟苯基二吡咯烷烃(1);1与3-氯-4-羟基苯甲醛经缩合反应合成了一个新的10-位苯环被氯原子取代的单羟基自由咔咯——10-(3-氯-4-羟苯基)-5,15-二(五氟苯基)咔咯(2),收率12.0%,其结构经UV-Vis,1H NMR,19F NMR,HR-ESI-MS和X-射线单晶衍射表征。琼脂糖凝胶电泳实验发现:2在光照下能够有效引起超螺旋质粒p BR 322 DNA发生断裂,当浓度为100μmol·L-1时,活性最强,断裂百分比为68%。 相似文献
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Melanie Schmidlehner Felix Faschinger Lorenz Michael Reith Martin Ertl Wolfgang Schoefberger 《应用有机金属化学》2013,27(7):395-405
In this study, novel water‐soluble corrole amino acid conjugates were synthesized and characterized. The coupling reaction of A2B‐ and A3‐corroles with glycine ethyl ester and taurine under strong basic conditions proved to be successful and yielded di‐ and trifunctionalized corrole amino acid conjugates in good yields. The subsequent metalation of the corrole/amino acid conjugates broadens the scope for applications considerably. As examples, we herein show the catalytic activity of the Mn(III) A3‐corrole towards O2 evolution. First we employed tert‐butyl hydroperoxide (t‐BuOOH) as oxidant to obtain the Mn(V)oxo species and tetrabutyl ammonium hydroxide (TBAH) as hydroxide donor agent. Furthermore, the binding properties of the non‐metalated and the Mn(III) A3‐corrole/amino sulfonic acid conjugates and transport of proteins were investigated and the conjugates exhibited binding to human serum albumin (HSA). Finally, a novel Ga(III) A3‐corrole/amino sulfonic acid derivative was synthesized and we briefly describe the photophysical properties of this compound. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
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Lan Yu Qi Wang Lu Dai Wei-Ying Li Rong Chen Mian HR Mahmood Hai-Yang Liu Chi-Kwong Chang 《中国化学快报》2013,24(6):447-449
Pseudo-first order reaction rate constants of 5,10,15-tris(pentafluorophenyl)corrole Mn(V)-oxo (F15CMn(V)-oxo),5,15-bis(pentafluorophenyl)-10-(phenyl)corrole Mn(V)-oxo(F10CMn(V)-oxo),5,15- bis(phenyl)-10-(pentafluorophenyl)corrole Mn(V)-oxo(F5CMn(V)-oxo) and 5,10,15-tris(phenyl)corrole Mn(V)-oxo(F0CMn(V)-oxo) with a series of alkene substrates in different solvents were determined by UV-vis spectroscopy.The results indicated that the oxygen atom transfer pathway between Mn(V)-oxo corrole and alkene is solvent-dependent. 相似文献
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Catarina I. V. Ramos M. Graça Santana‐Marques A. J. Ferrer‐Correia Joana F. B. Barata Augusto C. Tomé M. Graça P. M. S. Neves J. A. S. Cavaleiro Paulo E. Abreu Mariette M. Pereira Alberto A. C. C. Pais 《Journal of mass spectrometry : JMS》2012,47(4):516-522
Two new isomeric aminomethyl corrole derivatives of [5,10,15‐tris(pentafluorophenyl)corrolato]gallium(III) were synthesized with pyridine (py) molecules as axial ligands. When investigated by electrospray ionization mass spectrometry, in the positive and the negative ion modes, these compounds showed an unusual gas‐phase behavior that could be used for their differentiation. In the positive ion mode, the differentiation was achieved through the formation of diagnostic fragment ions formed from [M‐py + H]+ precursors, by (CH3)2NH and HF losses. An unusual addition of water to the main fragment ions provides an alternative route for isomer identification. Semi‐empirical calculations were performed to elucidate the structures and stabilities of the main ionic species formed in the positive ion mode. In the negative ion mode isomer discrimination is accomplished via the fragmentation of the methoxide adduct ions [M‐py + CH3O]‐ through (CH3)2 N. and HF losses. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
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Yanming Zhao Wenhao Dai Yunlei Peng Zheng Niu Qi Sun Chuan Shan Hui Yang Gaurav Verma Lukasz Wojtas Daqiang Yuan Zhenjie Zhang Haifeng Dong Xueji Zhang Bao Zhang Yaqing Feng Shengqian Ma 《Angewandte Chemie (International ed. in English)》2020,59(11):4354-4359
Herein, for the first time, we present the successful synthesis of a novel two‐dimensional corrole‐based covalent organic framework (COF) by reacting the unusual approximately T‐shaped 5,10,15‐tris(p‐aminophenyl)corrole H3TPAPC with terephthalaldehyde, which adopts desymmetrized hcb topology and consists of a staggered AB stacking structure with elliptical pores. The resultant corrole‐based COF, TPAPC‐COF , exhibits high crystallinity and excellent chemical stability. The combination of extended π‐conjugated backbone and interlayer noncovalent π–π interactions endows TPAPC‐COF with excellent absorption capability in the entire visible‐light and even near‐infrared regions. Moreover, this work suggests the promise of TPAPC‐COF as a new class of photoactive material for efficient singlet‐oxygen generation with potential photodynamic therapy application as demonstrated by in vitro anticancer studies. 相似文献
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Dr. Abraham B. Alemayehu Dr. Hugo Vazquez-Lima Dr. Simon J. Teat Prof. Dr. Abhik Ghosh 《ChemistryOpen》2019,8(10):1298-1302
A combination of quantum chemical calculations and synthetic studies was used to address the possibility of very high (>6) valence states of transition metals in porphyrin-type complexes. With corrole as a supporting ligand, DFT calculations ruled out Re(VII) and Ir(VII) dioxo complexes as stable species. Attempted rhenium insertion into benzocarbaporphyrin (BCP) ligands on the other hand led to two products with different stoichiometries – Re[BCP]O and Re[BCP]O2. To our surprise, single-crystal structure determination of one of the complexes of the latter type indicated an ReVO center with a second oxygen bridging the Re−C bond. In other words, although the monooxo complexes Re[BCP]O are oxophilic, the BCP ligand cannot sustain a trans-ReVII(O)2 center. The search for metal valence states >6 in porphyrin-type ligand environments must therefore continue. 相似文献
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Hua-Bin CHEN Xiao-Hui ZHANG Li-Zhen GONG Jing HE Xuan XU Zhi-Guang XU Hai-Yang LIU 《物理化学学报》2016,32(8):1983-1989
采用含时密度泛函理论(TDDFT)和B3LYP方法对一系列β位咔咯锰(V)氧配合物的几何结构、前线轨道、自然键轨道和电子吸收光谱进行了计算。并探讨了β位取代基对咔咯锰(V)氧配合物电子吸收光谱的影响。结果显示β位取代基效应中的空间效应是能导致该体系电子吸收光谱Soret带和Q带红移。β位取代基的空间位阻大时,导致配合物的咔咯环产生严重扭曲,引起Soret带和Q带吸收峰的ΔE能隙减小,导致Soret带和Q带发生红移。 相似文献