Mn–O–O Electron Spin Flip Mechanism Triggered by the Visible-Light Irradiation for the Generation of an Active Mn(V)–Oxo Complex from O₂: Insight from Density Functional Calculations

Abstract

We reveal a new activation mechanism of O2 by electron spin flip for the formation of a high-valent Mn­(V)–oxo corrolazine complex under O2 atmosphere and visible-light irradiation conditions. Ab initio calculations show that a loosely associated triplet complex from a quintet manganese corrolazine with a triplet O2 is formed initially in reaction. The subsequent strong bonding interactions between dioxygen with the manganese corrolazine, triggered by the visible-light irradiation, give rise to an increase in orbital splitting energy and drive the spin flip of electrons located at Mn and their rearrangement among the frontier orbitals, yielding the radical-like [Mn]–O–O species with high reactivity, which can easily abstract the hydrogen of the substrate to form the high-valent Mn­(V)–oxo active oxidant through the following rebound reaction. Here the coupling interactions of d xz and d yz of Mn with the corresponding π xz 2 3 and π yz 2 3 orbitals of O2 may form two new extending π bonds, π xz 3 4 and π yz 3 4 . Such an increase of antibonding π electrons in the Mn–O–O moiety may further activate the Mn-bound dioxygen and facilitate the generation of the monomeric Mn­(V)–oxo complex through selective oxidation of alkanes to alcohols by the photoinduced radical-like [Mn]–O–O species.

The High-Effective Catalytic Degradation of Benzo[a]pyrene by Mn-Corrolazine Regulated by Oriented External Electric Field: Insight From DFT Study

“…In addition, the energy of structure 11 was the lowest, again proving that it was the most stable. Furthermore, Table 1 shows the bond lengths of Mn-O and O-O were 1.617 and1.265 Å, respectively, which are similar to the results obtained in our previous study ( Zhu et al, 2018 ), indicating that the [Mn]-O-O moiety in structure 11 has strong oxidation ability. Therefore, we chose structure 11 as the RC to further explore the degradation of BaP.…”

“…Our group has recently reported that Mn-corrolazine can activate oxygen in the air via an electron spin-flip mechanism under visible light irradiation, which forms a singlet [Mn]-O-O species with terminal radical characteristics ( Zhu et al, 2018 ). In fact, corrole has been widely used in many fields ( Zhu and Liang, 2015 ; Zhu et al, 2016 ; Li and Cao, 2018 ; Lvova et al, 2018 ; Liang et al, 2019 ; Zheng et al, 2020 ; Dedic et al, 2021 ; Li et al, 2021 ).…”

Oriented external electric fields regulating the oxidation reaction of CH4 catalyzed by Mn‐corrolazine

“…According to our previous studies, [46,[50][51][52] reaction. [52][53][54] Moreover, the reaction energy of 72.3 kcal/mol will promote the reaction to the right thermodynamically.…”

“…Prokop and Goldberg's experiment and our density functional theory (DFT) calculations show that the high-valence Mn(V)-oxo corrolazine complex can be conveniently formed by the oxidation of the Mn(III) corrolazine with O 2 under visible light irradiation, while organic substrates are oxidized through continuous H-abstraction and rebound processes. [45,46] Therefore, Mn corrolazine is of great significance in catalysis because it can directly use cost-effective, abundant, and environmentally friendly molecular O 2 as an oxidant. Moreover, in the process of Mn-corrolazine-catalyzed oxidation of organic substrates, the rate-determining step is through the Mn-corrolazine O O species bearing the instinct Mn O reaction axis.…”

Be2CO3F2 Monolayer: A Flexible Ultraviolet Nonlinear Optical Material via Rational Design

“…With sustained efforts of many scientists discovering 2D monolayer materials with remarkable properties, several chemical systems like group IV and group III–V element compounds and transition metal oxides have been considered as promising systems for searching 2D monolayer materials . With respect to monolayer materials, they reveal a good flexibility, large photoluminescence, , valley polarizations, strong exciton effects, , and strong SHG responses. As such, several applicable monolayers have been developed, including insulators (hexagonal boron nitride (h-BN)), semiconductors (MoS 2 , black phosphorus (BP), etc.…”