Nucleophilicity and Accessibility Calculations of Alkanolamines: Applications to Carbon Dioxide Absorption Reactions

被引：29

作者：

Jhon, Young H. ^{[1
]}

Shim, Jae-Goo ^{[2
]}

Kim, Jun-Han ^{[2
]}

Lee, Ji Hyun ^{[2
]}

Jang, Kyung-Ryong ^{[2
]}

Kim, Jaheon ^{[1
]}

机构：

[1] Soongsil Univ, Dept Chem, Seoul 156743, South Korea

[2] Korea Elect Power Res Inst, Global Environm Res Grp, Environm & Struct Lab, Taejon 305380, South Korea

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2010年 / 114卷 / 49期

关键词：

ELECTRONIC POPULATION ANALYSIS; REACTION-CENTER CONGESTION; MOLECULAR WAVE FUNCTIONS; ATOM FORCE-FIELD; AQUEOUS-SOLUTIONS; OVERLAP POPULATIONS; CHEMICAL-REACTIVITY; ORBITAL THEORY; BOND ORDERS; FREE-ENERGY;

D O I：

10.1021/jp105914c

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Both nucleophilicities and accessibilities of three alkanolamines [monoethanolamine (MEA), (2-(methylamino)ethanol (MAE), and 2-amino-2-methyl-l-propanol (AMP)] were calculated to predict their reactivities with CO2. After DFT geometry-optimization calculations, the global, group, and atomic nucleophilicities of each amine were obtained using MP2 quantum mechanical calculations. Only global nucleophilicity matched an experimental pK(a) order (MAE > AMP > MEA). However, it failed to predict the slow rate of the sterically hindered AMP and the order of rate constants, MAE > MEA > AMP. The accessibilities of amines to CO2 have been calculated by MD simulations by monitoring collisions at the reaction centers: N atoms in amines and C in CO2. The accessibility results indicate that global nucleophilicity needs quantitative correction for steric effects to predict better reactivities of amines with CO2.

引用

页码：12907 / 12913

页数：7

共 105 条

[61] ON THE NON-ORTHOGONALITY PROBLEM CONNECTED WITH THE USE OF ATOMIC WAVE FUNCTIONS IN THE THEORY OF MOLECULES AND CRYSTALS [J].