from first principles PP-I-1

PL-3Bio-Inspired Hydrocarbon Oxidations by Nonheme Iron CatalystsQue L.,Jr.Department of Chemistry and Center for Metals in Biocatalysis,University of Minnesota, Minneapolis, Minnesota 55105, USAlarryque@umn.eduInspired by the versatile oxidation chemistry catalyzed by nonheme iron enzymes, we havebeen investigating the iron-catalyzed oxidations of hydrocarbons. Highly stereoselective cisdihydroxylationof olefins has been observed with the use of nonheme iron(II) complexeswith H 2 O 2 as oxidant. Insights into the catalytic mechanism have been obtained from acombination of product distribution studies, 18 O labeling experiments, and kinetic analysis aswell as DFT calculations. These results implicate a high-valent iron-based oxidant.Hydrocarbon oxidation can also be observed for iron complexes supported bytris(pyrazolyl)borate ligands that activate O 2 . A high-valent iron-based oxidant is alsopostulated for these reactions, which exhibit shape selectivity. The unusual shape selectivityobserved suggests that substrate recognition can be elicited even in a biomimetic complex ofrelatively simple design.9