Understanding the mechanism of H(+)-induced demetalation as a design strategy for robust iron(III) peroxide-activating catalysts.
نویسندگان
چکیده
The FeIII-TAML (tetra-amido macrocyclic ligand) activators 1 (Y = Cl) and 2 (Y = H2O), a (R = Me, X = H), b (Me, Cl), c (Me, MeO), d (Et, Cl), e (F, H), f (F, Cl), are five-coordinated in the solid state (X-ray crystallography) but are six-coordinated species in water with two H2O axial ligands. The first pKa's of aqueous ligands are in the range of 9.5-10.5. The acid-induced demetalation of 2 follows the equation kobs = k1*[H+] + k3*[H+]3. The rate constants k1* and k3* vary by 5 and 11 orders of magnitude depending on the nature of substituents R. The highest stabilization against the demetalation is achieved for R = F.
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ورودعنوان ژورنال:
- Journal of the American Chemical Society
دوره 125 41 شماره
صفحات -
تاریخ انتشار 2003