Journal of the American Chemical Society, Vol.119, No.30, 7030-7047, 1997
Synthesis, Reactivity, and Catalytic Behavior of Iron/Zinc-Containing Species Involved in Oxidation of Hydrocarbons Under Gif-Type Conditions
The present study explores the nature and reactivity of iron- and zinc-containing species generated in hydrocarbon-oxidizing Gif(IV)-type solutions Fe catalyst/Zn/O-2 in pyridine/acetic acid (10:1 v/v). The ultimate goal of this investigation is to unravel the role of metal sites in mediating dioxygen-dependent C-H activation, which in the case of Gif chemistry demonstrates an enhanced selectivity for the ketonization of secondary carbons. Reaction of [Fe3O(O2CCH3)(6)(PY)(3)]. Py (1) with zinc powder in CH3CN/CH3COOH or CH2Cl2/CH3COOH affords the trinuclear compound [Zn2FeII(O2CCH3)(6)(py)(2)] (2). Single-crystal X-ray analysis confirms that one monodentate and two bidentate acetate groups bridge adjacent pairs of metals with the iron atom occupying a centrosymmetric position.
Keywords:COLI RIBONUCLEOTIDE REDUCTASE;TYROSYL RADICAL-DIIRON(III) COFACTOR;SOLUBLE METHANE MONOOXYGENASE;LINEAR TRINUCLEAR COMPLEXES;ZINC CARBOXYLATE COMPLEXES;IRON PORPHYRIN COMPLEXES;C-H BOND;SATURATED-HYDROCARBONS;ALKANE FUNCTIONALIZATION;MOLECULAR-OXYGEN