Nonheme Mononuclear and Dinuclear Iron(II) and Iron(III) Fluoride Complexes and Their Fluorine Radical Transfer Reactivity.

The nonheme iron(II) complexes containing a fluoride anion, Fe(BNPAO)(F) () and [Fe(BNPAOH)(F)(THF)](BF) (), were synthesized and structurally characterized. Addition of dioxygen to either or led to the formation of a fluoride-bridged, dinuclear iron(III) complex [Fe(BNPAO)(F)(μ-F)] (), which was characterized by single-crystal X-ray diffraction, H NMR, and elemental analysis. An iron(II)(iodide) complex, Fe(BNPAO)(I) (), was prepared and reacted with O to give the mononuclear complex -Fe(BNPAO)(OH)(I) ().

Selective Radical Transfer in a Series of Nonheme Iron(III) Complexes.

A series of nonheme iron complexes, Fe(BNPAO)(L)(L) (L = N, NCS, NCO, and Cl) have been synthesized using the previously reported BNPAO ligand. The ferrous analogs Fe(BNPAO)(L) (L = N, NCS, and NCO) were also prepared. The complexes were structurally characterized using single crystal X-ray diffraction, which shows that all the Fe complexes are six-coordinate, with one anionic ligand (L) in the H-bonding axial site and the other anionic ligand (L) in the equatorial plane, cis to the L ligand.

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

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.