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

Abstract

Mn-corrolazine-catalyzed CH 4 oxidation, as well as the regulation of its oriented external electric fields (OEEFs), is systematically studied using the first-principle calculations. Extensive density functional calculations show that the activation energy of CH 4 oxidation catalyzed by Mn-corrolazine is up to 38.5 kcal/mol in the field-free condition. However, when the OEEF is applied, the reactant and the transition state of the oxidation reaction are stabilized, originating from an attractive interaction between the increased dipole moment and the applied fields. Furthermore, when the field is negative, the activation energy decreases as the field increases. Especially for the negative field along the intrinsic Mn O reaction axis perpendicular to the corrolazine ring, of which the orientation is easily aligned in practical applications, when its intensity reaches −0.015 a.u., the activation energy of CH 4 oxidation is reduced to 25.0 kcal/mol. K E Y W O R D S catalysis, CH 4 oxidation, density functional theory calculations, Mn-corrolazine, oriented external electric field 1 | INTRODUCTION Searching for novel and efficient catalysts has always been the most important subject in chemical research. Traditionally, the common catalysts are molecules and the surfaces or interface in homogeneous and heterogeneous systems, [1-6] respectively. However, in recent years, many new technologies, such as ultrasound, [7] microwaves, [8] mechanical stress, [9] and nanoreactors, [10] have been used to control various reaction processes as novel catalysts. Electrostatic forces play an extremely important role in chemical reactions involving the arrangement of nuclei and electrons. [11-13] A typical example is the electrostatic catalysis of enzymes in nature. [10,14-16] The polar environment originating from the subtle arrangement of atoms around the active site produces the electric field that can efficiently and selectively catalyze various biochemical reactions. Using the same idea, research is increasingly focused on regulating the stability of the reactants and transition states, as well as products, using artificial external electric fields through dipole-field interaction, thereby manipulating the chemical reaction process. [17-44] Very recently, Shaik et al. performed a much computational research to explore the effect of oriented external electric fields (OEEFs) on organic reactions. [17-23] Their research results show that OFFEs along the reaction axis involving the electron transfer can significantly catalyze the organic reactions, while the OFFEs along other directions can control the regioselectivity and stereoselectivity, and some results are confirmed by experimental evidence provided by Aragonès et al. [18] However, although great progress has been made in both the experimental and theoretical research, [17-24,27,30] a major problem in using the OFFEs to manipulate reaction processes is to deliver the external electric fields and orient the molecules within the applied fields simultaneously. The corrole, a porph...

OEEFs precisely regulating the propane oxidation reaction catalyzed by O–Fe-corrolazine

“…Based on our previous research results, 48,49 the ground state of O-Fe-corrolazine is a quartet state, which exhibits excellent activation ability for the C-H bond in the methane oxidation to methanol reaction. Moreover, its catalytic ability can be regulated by OEEFs.…”

“…Recently, our group reported that O-Fe-corrolazine can catalyze methane oxidation under mild conditions through the rebound mechanism and found that the reaction barrier can be effectively regulated by OEEFs. [48][49][50] As a novel kind of catalyst, OEEFs can effectively regulate various reactions through interactions with molecular dipole moments (D-M), which promotes or suppresses reactions, and can regulate regio-selectivity, stereo-selectivity, and spin selectivity. [51][52][53] Shaik et al conducted a lot of computational research on the effect of OEEFs on organic reactions [54][55][56][57][58] and found that organic reactions can be considerably promoted by OEEFs in the direction of the reaction axis, while regioselectivity and stereoselectivity can be modulated in other directions.…”

“…57 Our group also found that methane oxidation can be effectively regulated by OEEFs. 48,49 Here, to further expand the application of O-Fe-corrolazine and OEEFs, DFT was carried out to investigate the propane oxidation reaction catalyzed by O-Fe-corrolazine systematically. OEEFs were used to regulate the reaction activity and selectivity.…”

Oriented External Electric Fields Regurating the Reaction Mechanism of CH4 Oxidation Catalyzed by Fe(IV)-Oxo-Corrolazine: Insight from Density Functional Calculations

“…In particular, Fe(IV)-oxo porphyrin π-cation radical species, known as Cpd-I in heme proteins such as cytochrome P450, can mediate many key oxidative processes ( Meunier et al, 2004 ; Shaik et al, 2005 ; Cho et al, 2012 ; Zhang et al, 2017 ; Caddell Haatveit et al, 2019 ; Caulfield et al, 2019 ). Corrolazines, formed by replacing the meso-position carbon atoms of corroles with N atoms, are very similar in structure to porphyrins, but have more π electrons than porphyrins, and can better stabilize high-valent metals ( Ramdhanie et al, 2001 ; Goldberg et al, 2003 ; Fox et al, 2004 ; Lansky et al, 2005 ; Lansky and Goldberg, 2006 ; Goldberg 2007 ; McGown et al, 2009 ; Prokop et al, 2011 ; Pierloot et al, 2012 ; Baglia et al, 2015 ; Joslin et al, 2016 ; Jung et al, 2016 ; Zaragoza et al, 2016 ; Ghosh 2017 ; Zhu et al, 2018 ; Dedić et al, 2021 ; Wang et al, 2021 ; Zhu et al, 2021 ). As Fe is the active center metal of methane monooxygenase ( Shteinman 2020 ; Freakley et al, 2021 ), which can selectively convert methane to methanol under natural environmental conditions.…”

Deoxygenation reactions of nitrous oxide assisted by oriented external electric field

“…Strip out these reports, here, we tried a new strategy to reduce N 2 O with silanes via metal-free catalyst. It is known that oriented external electric field (OEEF) had been proved an effective, green, and controllable catalytic method, not only for the structures and properties of molecules, but also for the catalysis of chemical reactions [40][41][42][43][44][45][46][47][48]. In 2004, Shaik et al first reported that the OEEF could control the selectivity of iron-oxo porphyrin with propene [49].…”