Ferrous dipyrrin complexes have been shown to catalytically functionalize C-H bonds using organic azides as terminal oxidants. Isolation of a catalytically active intermediate has permitted structural and electronic characterization of a unique high-spin iron(III)-iminyl featuring antiferromagnetic coupling between the metal center and an iminyl radical.  Our present efforts are focused on understanding how electronic structure permits C-H functionalization reactivity via synthesis of iron-dipyrrinato complexes in varied oxidation states bearing terminal imido ligands. The described complexes have been characterized by single crystal X-ray diffraction, electron paramagnetic resonance, 57Fe Mossbauer, magnetometry, voltammetry, computational methods, and reactivity towards substrate in an effort to ascertain the essential elements for direct C-H amination chemistry from an electronic standpoint. This work represents an effort to provide the basis for developing more active and/or robust C-H bond functionalization catalysts.

Electronic structure of iron complexes competent for C-H functionalization

248th National Meeting (2014)

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