Coupling of Methane and Carbon Dioxide Mediated by Diatomic Copper Boride Cations

Chen, Qiang; Zhao, Yan‐Xia; Jiang, Lixue; Chen, Jiaojiao; He, Sheng‐Gui

doi:10.1002/anie.201808780

Cited by 35 publications

(24 citation statements)

References 85 publications

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“…+ + CH4 and CuB + + CH4 is very instructive for the further study of the reactions between new transition-metal borides and methane. In both VB3 + and CuB + systems 42,43 , only the B atom is involved in the activation of the first C-H bond. For the VB + system, the H3C-H cleavage mainly takes place at the V-side through the synergistic insertion of V-B unit into the C-H bond.…”

Section: Fig 4 Dft Calculated Potential Energy Curves (Pecs) For Spimentioning

confidence: 99%

“…Recently, transition-metal boride cations have been discovered as a new category of active species for the thermal activation of methane 42,43 . Inspired by these findings, the diatomic vanadium boride cation (VB + ) has been studied to explore the feasibility of the early 3d transition-metal atom participating in the C-H bond activation of methane.…”

Section: Introductionmentioning

confidence: 99%

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Thermal Activation of Methane by Diatomic Vanadium Boride Cations

Chen¹,

中国科学院化学研究所²,

Jiang³

et al. 2019

Acta Physico-Chimica Sinica

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Methane activation by transition metal species has been extensively investigated over the past few decades. It is observed that ground-state monocations of bare 3d transition metals are inert toward CH4 at room temperature because of unfavorable thermodynamics. In contrast, many mono-ligated 3d transition metal cations, such as MO + (M = Mn, Fe, Co, Cu, Zn), MH + (M = Fe, Co), and NiX + (X = H, CH3, F), as well as several bis-ligated 3d transition metal cations including OCrO + , Ni(H)(OH) + , and Fe(O)(OH) + activate the C-H bond of methane under thermal collision conditions because of the pronounced ligand effects. In most of the abovementioned examples, the 3d metal atoms are observed to cooperate with the attached ligands to activate the C-H bond. Compared to the extensive studies on active species comprising of middle and late 3d transition metals, the knowledge about the reactivity of early 3d transition metal species toward methane and the related C-H activation mechanisms are still very limited. Only two early 3d transition metal species HMO + (M = Ti and V) are discovered so far to activate the C-H bond of methane via participation of their metal atoms. In this study, by performing mass spectrometric experiments and density functional theory calculations, we have identified that the diatomic vanadium boride cation (VB +) can activate methane to produce a dihydrogen molecule and carbon-boron species under thermal collision conditions. The strong electrostatic interaction makes the reaction preferentially proceed the V side. To generate experimentally observed product ions, a two-state reactivity scenario involving spin conversion from high-spin sextet to low-spin quartet is necessary at the entrance of the reaction. This result is consistent with the reported reactions of 3d transition metal species with CH4, in which the C-H bond cleavage generally occurs in the low-spin states, even if the ground states of the related active species are in the high-spin states. For VB + + CH4, the insertion of the synergetic V-B unit (rather than a single V or B atom) into the H3C-H bond causes the initial C-H bond activation driven by the strong bond strengths of V-CH3 and B-H. The mechanisms of methane activation by VB + discussed in this study may provide useful guidance to the future studies on methane activation by early transition metal systems.

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Section: Fig 4 Dft Calculated Potential Energy Curves (Pecs) For Spimentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Thermal Activation of Methane by Diatomic Vanadium Boride Cations

Chen¹,

中国科学院化学研究所²,

Jiang³

et al. 2019

Acta Physico-Chimica Sinica

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“…The nucleophilicity of gold is important in oxidative reactions, the Au − anion is more nucleophilic than Au(0), Au(I), and Au(III) species, and thus reactions of atomic Au − anions with hydrocarbons in the gas phase were studied [ 14 , 19 ]. The study of gas-phase ion-molecule reactions provides mechanistic insights into the bond-breaking and -making steps that are often obscured under condensed-phase environments, which are complicated by solvents, counterions, and ligands [ 14 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 ]. Although gas-phase obtained information cannot replace that of the condensed phase, understanding the intrinsic unit makes it more feasible to improve chemical reactions or catalysts from a bottom-up approach [ 20 , 22 , 26 , 30 , 31 ].…”

Section: Introductionmentioning

confidence: 99%

Computational Studies of Coinage Metal Anion M− + CH3X (X = F, Cl, Br, I) Reactions in Gas Phase

Wang

Ying

et al. 2022

Molecules

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We characterized the stationary points along the nucleophilic substitution (SN2), oxidative insertion (OI), halogen abstraction (XA), and proton transfer (PT) product channels of M− + CH3X (M = Cu, Ag, Au; X = F, Cl, Br, I) reactions using the CCSD(T)/aug-cc-pVTZ level of theory. In general, the reaction energies follow the order of PT > XA > SN2 > OI. The OI channel that results in oxidative insertion complex [CH3–M–X]− is most exothermic, and can be formed through a front-side attack of M on the C-X bond via a high transition state OxTS or through a SN2-mediated halogen rearrangement path via a much lower transition state invTS. The order of OxTS > invTS is inverted when changing M− to Pd, a d10 metal, because the symmetry of their HOMO orbital is different. The back-side attack SN2 pathway proceeds via typical Walden-inversion transition state that connects to pre- and post-reaction complexes. For X = Cl/Br/I, the invSN2-TS’s are, in general, submerged. The shape of this M− + CH3X SN2 PES is flatter as compared to that of a main-group base like F− + CH3X, whose PES has a double-well shape. When X = Br/I, a linear halogen-bonded complex [CH3−X∙··M]− can be formed as an intermediate upon the front-side attachment of M on the halogen atom X, and it either dissociates to CH3 + MX− through halogen abstraction or bends the C-X-M angle to continue the back-side SN2 path. Natural bond orbital analysis shows a polar covalent M−X bond is formed within oxidative insertion complex [CH3–M–X]−, whereas a noncovalent M–X halogen-bond interaction exists for the [CH3–X∙··M]− complex. This work explores competing channels of the M− + CH3X reaction in the gas phase and the potential energy surface is useful in understanding the dynamic behavior of the title and analogous reactions.

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“…Chen et al. demonstrated the use of a diatomic species (CuB + ) to mediate the direct C−C coupling reaction between CH 4 and CO 2 . Our recent work has shown that the radical anion of CO 2 (i.e., CO 2 .− ) can be inserted into the C−H bond of C 6 H 6 and eventually lead to the formation of benzoic acid .…”

Section: Introductionmentioning

confidence: 99%

“…Chen et al demonstratedt he use of ad iatomic species (CuB + )t om ediate the directC ÀCc oupling reactionb etween CH 4 and CO 2 . [11] Our recentw ork has shown that the radical anion of CO 2 (i.e., CO 2 C À )c an be insertedi nto the CÀHb ond of C 6 H 6 and eventually lead to the formation of benzoic acid. [12] These findings suggest that ions, either cations or anions, in the gas phase may provide an alternative environment for CO 2 activation.A lthough af ree electron can easily activate CO 2 to form the radical anion CO 2 C À ,i ti sv ery difficult to manipulate CO 2 C À as ar eactanto ra ni nitiator of radical reactions due to its very short lifetime.…”

Section: Introductionmentioning

confidence: 99%

Electride‐Sponsored Radical‐Controlled CO₂Reduction to Organic Acids: A Computational Design

Tang

Zhou

et al. 2020

Chemistry A European J

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Converting CO 2 into high-value chemicals has been regardeda sa nimportant solution for as ustainable low-carbon economy.I nt his work, we have theoretically designed an innovative strategy for the absorptiona nd activation of CO 2 by the electride N3Li, that is,1 ,3,5(2,6)-tripyridinacyclohexaphane (N3) intercalated by lithium.D FT computations showed that the interaction of CO 2 with N3Li leads to the catalytic complex N3Li(h 2 -O 2 C), which can initiate the radical-controlled reduction of anotherC O 2 to form organic acids through radical reactions in the gas phase. The CO 2 reductionc onsists of four steps:( 1) The formation of N3Li(h 2 -O 2 C) through the combinationo fN 3Li and CO 2 ,(2) hydrogen abstraction from RH (R = H, CH 3 ,a nd C 2 H 5 )b yN 3Li(h 2 -O 2 C) to form the radical RC and N3Li(h 2 -O 2 C)H, (3) the combination of CO 2 and the radicalRC to form RCOOC,and (4) intermolecular hydrogen transferf rom the intermediateN 3Li(h 2 -O 2 C)H to RCOOC.I nt he whole reactionp rocess, the CO 2 moiety in the complex N3Li(h 2 -O 2 C) maintains ac ertainr adical character at the carbon atom of CO 2 and plays as elf-catalyzing role. This work represents the first example of electridesponsored radical-controlledC O 2 reduction,a nd thus provides an alternative strategy for CO 2 conversion.

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Coupling of Methane and Carbon Dioxide Mediated by Diatomic Copper Boride Cations

Cited by 35 publications

References 85 publications

Thermal Activation of Methane by Diatomic Vanadium Boride Cations

Thermal Activation of Methane by Diatomic Vanadium Boride Cations

Computational Studies of Coinage Metal Anion M− + CH3X (X = F, Cl, Br, I) Reactions in Gas Phase

Electride‐Sponsored Radical‐Controlled CO₂Reduction to Organic Acids: A Computational Design

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Coupling of Methane and Carbon Dioxide Mediated by Diatomic Copper Boride Cations

Cited by 35 publications

References 85 publications

Thermal Activation of Methane by Diatomic Vanadium Boride Cations

Thermal Activation of Methane by Diatomic Vanadium Boride Cations

Computational Studies of Coinage Metal Anion M− + CH3X (X = F, Cl, Br, I) Reactions in Gas Phase

Electride‐Sponsored Radical‐Controlled CO2Reduction to Organic Acids: A Computational Design

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Electride‐Sponsored Radical‐Controlled CO₂Reduction to Organic Acids: A Computational Design