去质子化咔咯内氢迁移反应的理论研究
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摘要
采用B3LYP/6-31G~(**)方法在Gaussian09程序下,对去质子化咔咯(CH_2~-)体系进行结构优化和振动分析。结果显示,CH_2~-的四种不同构型稳定性差异是由内氢原子间距决定的,内氢原子间距大,相对能量低,稳定性高。优化不同构型间相互转化的内氢迁移(IHAT)反应的过渡态,并进行相关的比较计算,各过渡态的能量高低也与内氢原子间距密切相关。CH_2~-的各构型能量差异大于PH_2,同样是从能量最低到能量最高的稳定构型的内氢迁移反应,CH2-的正逆反应速率的差异明显大于PH_2。
The structures and energies of reactant,product,transition states of the inner transfer reactions( IHAT) of hydrogen atoms in deprotonated corrole( CH_2~-) are studied. The B3LYP/6-31 G** method is carried out using Gaussian 09 software. The relative stability of isomers and transition states depends on the distances of inner hydrogen atoms. The distance is longer,the relative energy is lower and relative stability is better. The calculated results show that the difference between of positive and inverse reaction speeds of trans→cis reactions of CH_2~- are higher than that of porphine( PH_2).
The structures and energies of reactant,product,transition states of the inner transfer reactions( IHAT) of hydrogen atoms in deprotonated corrole( CH_2~-) are studied. The B3LYP/6-31 G** method is carried out using Gaussian 09 software. The relative stability of isomers and transition states depends on the distances of inner hydrogen atoms. The distance is longer,the relative energy is lower and relative stability is better. The calculated results show that the difference between of positive and inverse reaction speeds of trans→cis reactions of CH_2~- are higher than that of porphine( PH_2).
引文
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廖玉婷,马思渝.2003.卟吩内氢迁移反应的理论研究[J].化学学报,61(8):1226-1231.
廖玉婷,饶火瑜,孔凡峰,等.2005.卟啉内氢迁移反应氟取代基效应的理论研究[J].化学物理学报,18(5):750-758.
廖玉婷,饶火瑜,王海江,等.2011.单取代氧/硫杂紫菜嗪内氢迁移反应的理论研究[J].计算机与应用化学,28(11):1445-1450.
廖玉婷,饶火瑜,曾宏俊,等.2006b.氧/硫杂卟啉内氢迁移反应的理论研究[J].化学学报,64(21):2318-2144.
廖玉婷,饶火瑜,王秋月,等.2012.Corrole和Corrolazine的结构及其内氢迁移反应的理论研究[J].计算机与应用化学,29(8):947-950.
刘晶晶,汪华华,应晓,等.2011.Corrole锰-氧配合物的稳定性研究[J].高等学校化学学报,32(2):218-224.
刘香帅,雷娥,李文,等.2018.扩展卟啉Ni(Ⅱ),Pd(Ⅱ)和Pt(Ⅱ)单金属配合物光电性质的理论研究[J].分子科学学报,34(2):170-176.
马思渝,廖玉婷.2003.卟吩结构的理论方法和基组效应[J].北京师范大学学报(自然科学版),39(1):107-114.
张燕伟,史蕾,沈涵,等.2008.5,10,15-三(五氟苯基)Corrole及其相似卟啉化合物的光物理特性[J].光学学报,28(12):2375-2378.
Gross Z,Galili N,Saltsman I.1999.The First Direct Synthesis of Corroles from Pyrrole[J].Angew.Chem.Int.Ed.,38(10):1427-1429.
Gryko D T,Jadach K.2001.A simple and versatile one-pot synthesis of meso-substituted trans-A2B-corroles[J].J.Org.Chem.,66:4267-4275.
Haddad R E,Gazeau S,Pecaut J,et al.2003.Origin of the Red Shifts in the Optical Absorption Bands of Nonplanar Tetraalkylporphyrins[J].J.Am.Chem.Soc.,125:1253-1257.
Hunter C A,Sanders K M.1990.The nature of.pi.-.pi.interactions[J].J.Am.Chem.Soc,112(14):5525-5534.
Johnson A W,Kay I T.1965.306.Corroles.Part I.Synthesis[J].J.Chem.Soc.1620-1629.
Liu H Y,Lai T S,Yeung L L,et al.2003.First synthesis of perfluorinated corrole and its Mn=o complex[J].Org.Lett.,5(5):617-620.
Mahammed A,Weaver J J,Gtay H B,et al.2003.How acidic are corroles and why?[J].Tetrahedron Lett.,44:2077-2079.