Theoretical Study on the C-H Activation in Decarbonylation of Acetaldehyde by NiL_2(L=SO_3CH_3) Using Density Functional Theory  

作　　者：刘红飞 JIA Tiekun MIN Xinmin 

机构地区：[1]State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology [2]School of Physics and Electrical Information Engineering, Ningxia University [3]Department of Materials Science and Engineering, Luoyang Institute of Science and Technology

出　　处：《Journal of Wuhan University of Technology(Materials Science)》2014年第6期1170-1172,共3页武汉理工大学学报（材料科学英文版）

基　　金：Funded by the National Natural Science Foundation of China(No.51174179)

摘　　要：Density functional theory calculations were carried out to explore the potential energy surface（PES） associated with the gas-phase reaction of Ni L2（L=SO3CH3） with acetone. The geometries and energies of the reactants, intermediates, products and transition states of the triplet ground potential energy surfaces of [Ni, O, C2, H4] were obtained at the B3LYP/6-311＋＋G（d,p） levels in C,H,O atoms and B3LYP/ Lanl2 dz in Ni atom. It was found through our calculations that the decabonylation of acetaldehyde contains four steps including encounter complexation, C-C activation, aldehyde H-shift and nonreactive dissociation. The results revealed that C-C activation induced by Ni L2（L=SO3CH3） led to the decarbonylation of acetaldehyde.Density functional theory calculations were carried out to explore the potential energy surface（PES） associated with the gas-phase reaction of Ni L2（L=SO3CH3） with acetone. The geometries and energies of the reactants, intermediates, products and transition states of the triplet ground potential energy surfaces of [Ni, O, C2, H4] were obtained at the B3LYP/6-311＋＋G（d,p） levels in C,H,O atoms and B3LYP/ Lanl2 dz in Ni atom. It was found through our calculations that the decabonylation of acetaldehyde contains four steps including encounter complexation, C-C activation, aldehyde H-shift and nonreactive dissociation. The results revealed that C-C activation induced by Ni L2（L=SO3CH3） led to the decarbonylation of acetaldehyde.

关 键 词：density functional theory decarbonylation transition state energy C-C activation 

分 类 号：O623.511[理学—有机化学]