Near-stoichiometric conversion of H(2)O(2) to Fe(IV)=O at a nonheme iron(II) center. Insights into the O-O bond cleavage step.

ABSTRACT: Near-quantitative formation of an oxoiron(IV) intermediate [Fe(IV)(O)(TMC)(CH(3)CN)](2+) (2) from stoichiometric H(2)O(2) was achieved with [Fe(II)(TMC)](2+) (1) (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraaza-cyclotetradecane). This important outcome is best rationalized by invoking a direct reaction between 1 and H(2)O(2) followed by a heterolytic O-O bond cleavage facilitated by an acid-base catalyst (2,6-lutidine in our case). A sizable H/D KIE of 3.7 was observed for the formation of 2, emphasizing the importance of proton transfer in the cleavage step. Pyridines with different pK(a) values were also investigated, and less basic pyridines were found to function less effectively than 2,6-lutidine. This study demonstrates that the reaction of Fe(II) with H(2)O(2) to form Fe(IV)= O can be

SUBMITTER: Li F 

PROVIDER: S-EPMC2823852 | biostudies-literature | 2010 Feb

REPOSITORIES: biostudies-literature