The Amazing High-Valent Nonheme Iron-Oxo Landscape

抄録

The investigation of synthetic nonheme oxoiron(IV) complexes has been stimulated by the trapping of such intermediate species in the catalytic cycles of several dioxygen activating nonheme iron enzymes, thus capturing the interests of many scientists. Since 2003 when the first crystal structure of a nonheme oxoiron(IV) complex was reported, over seventy such coordination complexes have been characterized. They exhibit a broad range of thermal stabilities, with some having a fleeting existence at room temperature to one with a half-life of 120 hours. Herein we provide an overview of the remarkable progress made in this area over the past thirteen years and demonstrate the central role coordination chemistry principles have played in achieving these advances. Very recently, progress has been made in synthesizing S = 2 oxoiron(IV) complexes that not only have spectroscopic parameters that come close to those associated with enzymatic oxoiron(IV) intermediates but also exhibit comparable reactivity in the cleavage of strong C–H bonds. Moreover, we describe the first spectroscopic and functional model compounds for the nonheme iron halogenases, which catalyze the conversion of C–H to C–halogen bonds in the biosynthesis of some natural products.