High-Valent Manganese Corroles and the First Perhalogenated Metallocorrole Catalyst

Ab initio multiconfiguration reference perturbation theory calculations on the energetics of low-energy spin states of iron(III) porphyrins

“…In unpublished work (Ghosh A, Dey A, unpublished results) we have found that B3LYP calculations with comparable basis sets favor the diamagnetic Mn(V) state by a smaller margin of about 0.3 eV. In contrast, Gross, Shaik and co-workers [39] [40]. B3LYP calculations on Mn(corrolato)(O) predicts a closed-shell Mn(V) state as the ground state-a qualitatively correct result-but the Mn(IV)-oxo corrole p-cation radical states lie barely about 0.1-0.2 eV higher in energy [36].…”

Enhanced iron(III) corrole-catalyzed oxidations with iodobenzene diacetate: Synthetic and mechanistic investigations

“…Remarkably, Fe III (TPFC) performs as well as one of the best porphyrin catalysts known Fe III (TPFPP)Cl (TPFPP = tetrakis(pentafluorophenyl)porphinato) with respect to the epoxidation of cyclohexene under similar reaction conditions [27]. This catalytic activity (TOF) and product selectivity is a major improvement over previously reported metallocorrole catalysts [13,16] including perhalogenated Mn III (F 8 TPFC) [20] and Mn III (Br 8 TPFC) [19]. Epoxidation of cis-and trans-stilbenes afforded corresponding expoxides exclusively with complete stereoretention (entries 3 and 4).…”

“…Later, biomimetic oxidations with Mn III (TPFC) [13], albumin-conjugated manganese [17] and chromium corroles [18] were also studied by the same group of authors. Perhalogenation of the corrole macrocycle with bromine or fluorine results in increased reactivity for the corrole-manganese complexes under catalytic conditions with PhIO [19,20]. Recently, we reported aerobic oxidations catalyzed by a fluorinated iron(IV) -oxo biscorrole in a photo-disproportionation mechanism [21].…”

High-valent transition metal centers and noninnocent ligands in metalloporphyrins and related molecules: a broad overview based on quantum chemical calculations

“…Using the Gross corrole synthesis [61] and literature procedures for metal insertion [62,63], we have prepared a number of new free-base and high-valent transition metal corroles, which are shown in Fig. 3.…”