Nonheme Iron(III) Azide and Iron(III) Isothiocyanate Complexes: Radical Rebound Reactivity, Selectivity, and Catalysis.

Journal of the American Chemical Society(2022)

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摘要
The new nonheme iron complexes Fe(BNPAO)(N) (), Fe(BNPAO)(OH)(N) (), Fe(BNPAO)(OH) (), Fe(BNPAO)(OH)(NCS) (), Fe(BNPAO)(NCS) (), Fe(BNPAO)(NCS) (), and Fe(BNPAO)(N) () (BNPAO = 2-(bis((6-(neopentylamino)pyridin-2-yl) methyl)amino)-1,1-diphenylethanolate) were synthesized and characterized by single crystal X-ray diffraction (XRD), as well as by H NMR, Fe Mössbauer, and ATR-IR spectroscopies. Complex was reacted with a series of carbon radicals, ArC· (Ar = -X-CH), analogous to the proposed radical rebound step for nonheme iron hydroxylases and halogenases. The results show that for ArC· (X = Cl, H, Bu), only OH· transfer occurs to give ArCOH. However, when X = OMe, a mixture of alcohol (ArCOH) (30%) and azide (ArCN) (40%) products was obtained. These data indicate that the rebound selectivity is influenced by the electron-rich nature of the carbon radicals for the azide complex. Reaction of with PhC· in the presence of Sc or H reverses the selectivity, giving only the azide product. In contrast to the mixed selectivity seen for , the reactivity of -Fe(OH)(NCS) with the X = OMe radical derivative leads only to hydroxylation. Catalytic azidation was achieved with as catalyst, λ-azidoiodane as oxidant and azide source, and PhCH as test substrate, giving PhCN in 84% (TON = 8). These studies show that hydroxylation is favored over azidation for nonheme iron(III) complexes, but the nature of the carbon radical can alter this selectivity. If an OH· transfer pathway can be avoided, the Fe(N) complexes are capable of mediating both stoichiometric and catalytic azidation.
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radical rebound reactivity,complexes,ironiii,catalysis
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