原子与分子物理学报2017，Vol.34Issue(4)：637-643,7.DOI:10.3969/j.issn.1000-0364.2017.04.009
铱催化甲醇羰基化制乙酸循环反应的理论探究
Theoretical study for the catalytic cycles ofiridium-catalysed methanol carbonylation
摘要
Abstract
The carbonylation of methanol to acetic acid catalyzed by Ir(I)-complex has been investigated by using the B3LYP level of density functional theory, with the relativistic effective core potential (RECP) of basis sets (SDD) for Ir and I and the 6-311+G(2d,p) basis set for C, H and O.The geometries for reactants, the transition states and the products are completely optimized.All the transition states are verified by the vibrational analysis and the internal reaction coordinate (IRC) calculations.The energetic span model was applied in the anionic and neutral cycle reactions to obtain some kinetic information.The determining transition states and the determining intermediates were confirmed, and the TOFs along were calculated by the AUTOF program.A comparison of electric charge density between the trans-[Ir(CO)2I2]-and cis-[Ir(CO)2I2]-indicated that the electron-rich transition metal complexes have good catalytic function, this order agrees well with the postulate.关键词
甲醇羰基化/铱碘络合物/乙酸/密度泛函理论/转化频率Key words
Methanol carbonylation/Rh(I)-complex/Acetic acid/Density functional theory/Turnover frequency分类
化学化工引用本文复制引用
张建辉,冷艳丽,刘婧,刘佳,张明明..铱催化甲醇羰基化制乙酸循环反应的理论探究[J].原子与分子物理学报,2017,34(4):637-643,7.基金项目
甘肃省高等学校科研项目(2014A-138,2014B-136) （2014A-138,2014B-136）
兰州资源环境职业技术学院课题 (Z2013-03) （Z2013-03）
