Department of Chemistry and Nano Science, Ewha Womans University , Seoul 03760, Korea.
Department of Chemistry, Sookmyung Women's University , Seoul 04310, Korea.
J Am Chem Soc. 2017 Oct 18;139(41):14372-14375. doi: 10.1021/jacs.7b08161. Epub 2017 Oct 4.
A mononuclear nonheme iron(V)-imido complex bearing a tetraamido macrocyclic ligand (TAML), [Fe(NTs)(TAML)] (1), was oxidized by one-electron oxidants, affording formation of an iron(V)-imido TAML cation radical species, [Fe(NTs)(TAML)] (2); 2 is a diamagnetic (S = 0) complex, resulting from the antiferromagnetic coupling of the low-spin iron(V) ion (S = 1/2) with the one-electron oxidized ligand (TAML). 2 is a competent oxidant in C-H bond functionalization and nitrene transfer reaction, showing that the reactivity of 2 is greater than that of 1.
单核非血红素铁（V）-亚胺配合物带有一个四氨大环配体（TAML），[Fe（NTs）（TAML）]（1），被单电子氧化剂氧化，形成铁（V）-亚胺 TAML 阳离子自由基物种，[Fe（NTs）（TAML）]（2）；2 是一个抗磁性（S = 0）的配合物，这是由于低自旋铁（V）离子（S = 1/2）与单电子氧化配体（TAML）之间的反铁磁耦合所致。2 是 C-H 键官能化和氮烯转移反应的有效氧化剂，表明 2 的反应性大于 1。
