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

TitleSynthesis and Reactivity of a Low-Coordinate Iron(II) Hydride Complex: Applications in Catalytic Hydrodefluorination
Publication TypeJournal Article
Year of Publication2017
AuthorsHein, NM, Pick, FS, Fryzuk, MD
JournalINORGANIC CHEMISTRY
Volume56
Pagination14513-14523
Date PublishedDEC 4
ISSN0020-1669
Abstract

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 beta-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 pre-catalyst for catalytic hydro-defluorination of perfluorinated aromatics in the presence of silane. Kinetic studies indicated that the rate-determining step during catalysis involved silane.

DOI10.1021/acs.inorgchem.7b02199