次级球氢键对非血红素铁配合物中氧反应性的影响
Impact of Secondary Sphere Hydrogen Bonds on O Reactivity within a Nonheme Iron Complex.
作者信息
LaDuca Andrew R, Wilson Jessica R, Sarkar Writhabrata, Zeller Matthias, Szymczak Nathaniel K
机构信息
Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109, United States.
H.C. Brown Laboratory, Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, United States.
出版信息
J Am Chem Soc. 2025 Feb 12;147(6):5099-5105. doi: 10.1021/jacs.4c15153. Epub 2025 Feb 2.
Abstract
A nonheme iron complex bearing the tris(6-phenylamino-pyridyl)methylamine (TPA) ligand with appended hydrogen bond (H-bond) groups displays facile O reactivity to form a monomeric Fe(III)OH complex, which can release •OH rebound to a carbon radical. An analogous compound without H-bonds, based on tris(6-methylpyridyl)methylamine (TPA), exhibits minimal O reactivity, forming a Fe(III)(μ-O)(μ-OH) dimer, which also reacts with carbon-based radicals. The H-bonding system enables O binding and activation at weakly reducing nonheme iron complexes, highlighting a cooperative role of secondary sphere units to facilitate reactions at atypical redox environments.
摘要
一种带有三（6-苯基氨基吡啶基）甲胺（TPA）配体并带有附加氢键（H键）基团的非血红素铁配合物表现出对O的易反应性，形成单体Fe(III)OH配合物，该配合物可释放•OH并反弹至碳自由基。一种基于三（6-甲基吡啶基）甲胺（TPA）的无氢键类似化合物表现出最小的O反应性，形成Fe(III)(μ-O)(μ-OH)二聚体，该二聚体也与碳基自由基反应。氢键系统能够在弱还原的非血红素铁配合物处实现O的结合和活化，突出了二级配位层单元在非典型氧化还原环境中促进反应的协同作用。
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