摘要
研究了几种单齿和双齿含氮配体在氧化羰化反应中的助催化性能。从含氮配体的电子效应、空间效应等方面探讨了不同含氮配体在甲醇氧化羰化反应中助催化作用的差异。结果表明,在甲醇氧化羰化反应中,含氮配体的碱性、共轭体系的大小、分子骨架的刚性以及氢键等因素对原位配合催化剂的催化性能均有很大影响。配体的共轭体系越大,分子刚性越强,助催化性能越好;当配体存在分子间氢键时,其助催化性能明显下降。对于单齿含氮配体,当不存在分子间氢键时,pKa值在7左右表现出最佳助催化性能。
The promotion effects of N-donor ligands for catalytic oxidative carbonylation of methanol were studied. It was found that the base strength of ligands, the size of conjugated systems, the rigidity of skeletons and the hydrogen bonds between the ligands had remarkable influences on the calalytic performance for the oxidative carbonylation. The ligands with larger conjugated systems and rigid skeletons give better catalytic activities, and intermolecular hydrogen bonds between ligands greatly decrease promoting activities. For monodentate ligands without intermolecular hydrogen bonds, those with pK, 7 exhibit the best promoting activity.The mechanism of steric and electronic effects for the oxidative carbonylation of methanol in homogeneous system was discussed in detail.
出处
《应用化学》
CAS
CSCD
北大核心
2005年第9期997-1001,共5页
Chinese Journal of Applied Chemistry
关键词
含氮配体
空间结构
电子效应
氧化羰化
甲醇
N-donor ligand, steric effect, electronic effect, oxidative carbonylation, methanol
