A "Beheaded" TAML Activator: A Compromised Catalyst that Emphasizes the Linearity between Catalytic Activity and pK_a.

ABSTRACT: Studies of the new tetra-amido macrocyclic ligand (TAML) activator [Fe^III{(Me₂CNCOCMe₂NCO)₂CMe₂}OH₂]^- (4) in water in the pH range of 2-13 suggest its pseudo-octahedral geometry with two nonequivalent axial H₂O ligands and revealed (i) the anticipated basic drift of the first pK_a of water to 11.38 due to four electron-donating methyl groups alongside (ii) its counterintuitive enhanced resistance to acid-induced iron(III) ejection from the macrocycle. The catalytic activity of 4 in the oxidation of Orange II (S) by H₂O₂ in the pH range of 7-12 is significantly lower than that of previously reported TAML activators, though it follows the common rate law (v/[Fe^III

SUBMITTER: Mills MR 

PROVIDER: S-EPMC5479581 | biostudies-literature | 2016 Dec

REPOSITORIES: biostudies-literature