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Synthesis and Reactivity of a Low-Coordinate Iron(II) Hydride Complex: Applications in Catalytic Hydrodefluorination

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journal contribution
posted on 16.11.2017, 19:18 by Nicholas M. Hein, Fraser S. Pick, Michael D. Fryzuk
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.