High-valent transition metal corrolazines

Abstract

High-valent metalloporphyrin intermediates have been implicated as key players in numerous mechanistic proposals for both biological (e.g., heme protein) and synthetic porphyrin mediated transformations. However, the direct observation of these species is quite challenging because of the inherently short lifetimes of many of these metalloporphyrin intermediates. This review focuses on our own efforts to synthesize and study a new class of porphyrinoid compounds called corrolazines, which are designed to stabilize high-valent species for direct analysis. These compounds are related to corroles, which also exhibit the unusual ability to stabilize high oxidation states, and the reactivity and physical properties of relevant corrole and porphyrin analogs are compared with the appropriate corrolazines. The chemistry of Cu, Co, V, and Mn are highlighted, with a particular emphasis on the reactivity of high-valent manganese-oxo complexes.