Nitrogen Atom Transfer between Manganese Complexes of Salen, Porphyrin, and Corrole and Characterization of a (Nitrido)manganese(VI) Corrole

Abstract

The investigations of complete nitrogen atom transfer reactions from (nitrido)manganese(V) salen to manganese(III) complexes of porphyrins and corroles revealed that stabilization of the [Mn(N)]2+ moiety is in the order of corrole > porphyrin > salen. The first kinetic examination of this quite fundamental reaction exposed a large solvent effect on both the enthalpy and entropy activation energies. Oxidation of the (nitrido)manganese(V) corroles leads to the first (nitrido)manganese(VI) complexes that are coordinated by tetrapyrrolic ligands.

Laser Flash Photolysis Generation and Kinetic Studies of Corrole–Manganese(v)‐Oxo Intermediates

“…Importantly, the recent report of characterization of a corrole-manganese(vi)-nitrido species shows that such high oxidation state manganese species are accessible. [23] In the model in Figure 7, the oxidizing system could shuttle between (Cor)Mn IV and (Cor)Mn VI (O) cations after the initial oxidation of the (Cor)Mn III complex. In the LFP studies, where sacrificial oxidants are not present, the velocities of reactions would reflect the populations of (Cor)Mn VI (O) cations that are determined by the disproportionation equilibrium constant.…”

Theoretical Investigation on the Mechanism of Oxygen Atom Transfer between Two Non‐Heme Iron Centres

“…A large solvent effect on the completion of the reaction was also observed experimentally for the nitrogen atom transfer between different metal macrocycles. [7] Nevertheless, the key results are reproduced in a dielectric environment: 9,7 BN are local minima well higher in energy than isolated reactants. The dissociation barriers with respect to 9,7 BN remain the same regardless of the environmental perturbations.…”

“…[4][5][6] Apart from the oxygen atom transfer reactions between two non-heme iron complexes, nitrogen atom transfer between manganese complexes bearing different macrocycles have also been reported. [7] (1) Although transfer of the oxygen atom formally happens in hydroxylation reactions, [8] it is still remarkable that it happens between different catalysts. In order to elucidate the mechanism by which non-heme oxidoiron(IV) complexes transfer their oxygen atom to other non-heme iron(II) systems, we present here the first density functional theory studies into a non-heme (µ-oxido)diiron(III) complex and its dissociation patterns into the respective oxidoiron(IV) and iron(II) complexes.…”

Henry Taube: Inorganic Chemist Extraordinaire

“…There was immediate interest in this work in laboratories around the world because of the possibility of finding practical routes for N fixation. 100,101 With this impetus, work in the Taube laboratory was focused on N 2 reduction, which led to studies of ruthenium 102,103 and osmium 104,105 ammine complexes with N 2 and other small molecules. Armor and Taube characterized the kinetics and thermodynamics of the formation of the N 2 monomer and dimer, 91 as well as a highly unusual complex of nitrous oxide.…”