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Published on: February 20, 2020
Lewis Base-Enhanced C-H Bond Functionalization Mediated by a Diiron Imido Complex
Reilly K Gwinn1, Trevor P Latendresse2, Owen N Beck1
1Department of Chemistry, Virginia Tech, Blacksburg, Virginia 24061, United States.
Abstract:
Herein, we investigate the effects of ligand design on the nuclearity and reactivity of metal-ligand multiply bonded (MLMB) complexes to access an exclusively bimetallic reaction pathway for C-H bond functionalization. To this end, the diiron alkoxide [Fe2(PhDbf)2] (1) was treated with 3,5-bis(trifluoromethyl)phenyl azide to access the diiron imido complex [Fe2(PhDbf)2(μ-NC8H3F6)] (2a) that promotes hydrogen atom abstraction (HAA) from a variety of C-H and O-H bond containing substrates. A diiron bis(amide) complex [Fe2(PhDbf)2(μ-NHC8H3F6)(NHC8H3F6)] (3) was generated, prompting the isolation of the analogous bridging amide terminal alkoxide [Fe2(PhDbf)2(μ-NHC8H3F6)(OC19H15)] (4) and the asymmetric pyridine-bound diiron imido [Fe2(PhDbf)2(μ-NC8H3F6)(NC5H5)] (6a). We found that 6a is competent for toluene amination, indicating the effect of Lewis base-enhanced C-H bond functionalization. Mechanistic investigations suggest that the bimetallic bridging imido complex is the reactive intermediate as no monometallic species is detected during the time course of the reaction.
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