Department of Chemistry , The Johns Hopkins University , Baltimore , Maryland 21218 , United States.
J Am Chem Soc. 2019 Jul 3;141(26):10148-10153. doi: 10.1021/jacs.9b03329. Epub 2019 Jun 20.
A new tetradentate, monoanionic, mixed N/O donor ligand (BNPAO) with second coordination sphere H-bonding groups has been synthesized for stabilization of a terminal Fe(OH) complex. The complex Fe(BNPAO)(OTf) (1) reacts with O to give a mononuclear terminal Fe(OH) complex, Fe(OH)(BNPAO)(OTf) (2), both of which were characterized by X-ray diffraction, electrospray ionization mass spectrometry, UV-vis, H and F nuclear magnetic resonance, Fe Mössbauer, and electron paramagnetic resonance spectroscopies. Treatment of 2 with carbon radicals (ArC·) gives ArCOH and the Fe complex 1, in direct analogy with the elusive radical "rebound" process proposed for nonheme iron enzymes.
一种新的四齿、单核、混合 N/O 供体配体（BNPAO），具有第二配位球氢键基团，已被合成用于稳定末端 Fe(OH) 配合物。配合物 Fe(BNPAO)(OTf)（1）与 O 反应生成单核末端 Fe(OH) 配合物 Fe(OH)(BNPAO)(OTf)（2），两者均通过 X 射线衍射、电喷雾电离质谱、紫外-可见、H 和 F 核磁共振、Fe Mössbauer 和电子顺磁共振光谱进行了表征。用自由基（ArC·）处理 2 得到 ArCOH 和 Fe 配合物 1，与非血红素铁酶中提出的难以捉摸的自由基“反弹”过程直接类似。
