作者:Michael W. Nee、John R. Lindsay Smith
DOI:10.1039/a902636c
日期:——
The axial ligand of a series of iron(III) 5,10,15,20-tetramesitylporphyrin phenolate complexes was found to exchange with added carboxylic acids and alcohols. The rates of axial ligand exchange with carboxylic acids were found to be dependent on acidity of the carboxylic acid, basicity of the phenolate, and the steric bulk of both the carboxylic acid and the phenolate axial ligand. The rates of axial ligand exchange with alcohols were found to be dependent on the nucleophilicity of the alcohol, leaving group ability of the phenolate, and the steric bulk of both the alcohol and the phenolate axial ligand. Different mechanisms for ligand exchange are proposed for carboxylic acids and alcohols.
研究发现,一系列 5,10,15,20-四甲基
卟啉苯酚铁(III)配合物的轴
配体可与添加的
羧酸和醇发生交换。研究发现,轴
配体与
羧酸的交换速率取决于
羧酸的酸性、
苯酚的碱性以及
羧酸和
苯酚轴
配体的立体体积。研究发现,轴
配体与醇的交换速率取决于醇的亲核性、
酚酸酯的离去基团能力以及醇和
酚酸酯轴
配体的立体体积。针对
羧酸和醇提出了不同的
配体交换机制。