A low-coordinate iron hydride complex bearing an unsymmetrical NpN (enamido–phosphinimine) ligand scaffold was synthesized and fully characterized. Insertion reactivity with azobenzene, 3-hexyne, and 1-azidoadamantane was explored, and the isolated products were analogous to previously reported β-diketiminate iron hydride insertion products. Surprisingly, the NpN iron hydride displays unprecedented reactivity toward hexafluorobenzene, affording an NpN iron fluoride complex and pentafluorobenzene as products. The NpN iron hydride is a precatalyst for catalytic hydro-defluorination of perfluorinated aromatics in the presence of silane. Kinetic studies indicated that the rate-determining step during catalysis involved silane.

中文翻译：

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低配位氢化铁（II）配合物的合成和反应性：在催化加氢脱氟化氢中的应用

合成并充分表征了带有不对称NpN（酰胺基-膦亚胺）配体骨架的低配位氢化铁络合物。探索了与偶氮苯，3-己炔和1-叠氮基金刚烷的插入反应性，并且分离的产物类似于先前报道的β-二酮化氢化铁插入产物。出人意料的是，NpN氢化铁对六氟苯显示出空前的反应性，提供了NpN氟化铁络合物和五氟苯作为产物。NpN氢化铁是在硅烷存在下全氟化芳烃催化加氢脱氟化氢的预催化剂。动力学研究表明，催化过程中的速率确定步骤涉及硅烷。