Reductive Activation of Small Molecules by Anionic Coinage Metal Atoms and Clusters in the Gas Phase

Muramatsu, Satoru; Tsukuda, Tatsuya

doi:10.1002/asia.201901156

Cited by 10 publications

(4 citation statements)

References 72 publications

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“…Efforts were put to understanding the mechanisms and search for suitable catalysts for C−X bond activation [ 8 , 9 , 10 , 11 , 12 , 13 ]. The discovery of catalytic gold by Haruta et al stimulated the development of gold catalysts in the form of surfaces, nanoparticles, embedded clusters, and single atoms [ 14 , 15 , 16 , 17 , 18 ]. 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 ].…”

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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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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“…The gas‐phase studies also enlightened the principles of methane activation (and C–H activation in general) by metals, metal oxides, metal complexes, metal clusters, and others (Armentrout, 2017 ; Bohme & Schwarz, 2005 ; Dietl et al, 2012 ; Roithova & Schröder, 2010 ; Schwarz, 2011 , 2014 ; Schwarz et al, 2017 ; Zhou et al, 2016 ). Much like for methane activation, gas‐phase studies described principles of activation, reactivity, and transformation of other small molecules too (Blagojevic et al, 2019 ; Muramatsu & Tsukuda 2019 ). As a result, we obtained a detailed knowledge of molecular transformations and on whole catalytic cycles (Bozovic et al, 2010 ).…”

Section: Introductionmentioning

confidence: 99%

Ion spectroscopy in methane activation

Roithová

Bakker

2021

Mass Spectrometry Reviews

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This review is devoted to ion spectroscopy studies of complexes relevant for the understanding of methane activation with metal ions and clusters. Methane activation starts with the formation of a complex with a metal ion. The degree of the interaction between an intact methane molecule and the ion can be monitored by the perturbations of C-H stretch vibrations in the methane molecule. Binding mediated by the electrostatic interaction results in a η 3 type coordination of methane. In contrast, binding governed by orbital interactions results in a η 2 type coordination of methane. We further review the spectroscopic characterization of activation products of metal-methane reactions, such as the metal-carbene and carbyne products resulting from the interaction of selected 5d metals with methane.The focus of recent research in the field has shifted towards the investigation of interactions between methane and metal clusters. We show examples highlighting that metal clusters can be more reactive in methane activation reactions.

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“…We have been interested in increasing the application of the gas-phase cluster model. − Studying the reaction mechanism using the gas-phase cluster may help us deepen the understanding of the reactions at the molecular level and help us design catalysts with tailored performance. − It may be interesting to answer the questions: whether the small sulfide clusters with particular size and stoichiometry have the potential to be better catalysts, especially when the studies of single-cluster catalysts (SCC) and gas-phase cluster catalysts have attracted much attention. − In our early work, theoretical studies on the geometric and electronic structures of MoS n –/0 ( n = 1–5) clusters have been carried out . In this study, we carried out the theoretical calculations of the H 2 S decomposition reaction with MS 3 (M = Mo, W) clusters.…”

Section: Introductionmentioning

confidence: 99%

Exploring the Reaction Mechanism of H₂S Decomposition with MS₃ (M = Mo, W) Clusters

Wang

Zhang

et al. 2020

ACS Omega

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H 2 S is abundantly available in nature, and it is a common byproduct in industries. Molybdenum sulfides have been proved to be active in the catalytic decomposition of hydrogen sulfide (H 2 S) to produce hydrogen. In this study, density functional theory (DFT) calculations are carried out to explore the reaction mechanisms of H 2 S with MS 3 (M = Mo, W) clusters. The reaction mechanism of H 2 S with MoS 3 is roughly the same as that of the reaction with WS 3 , and the free-energy profile of the reaction with MoS 3 is slightly higher than that of the reaction with WS 3 . The overall driving forces (−ΔG) are positive, and the overall reaction barriers (ΔG b ) are rather small, indicating that such H 2 productions are product-favored. MS 3 (M = Mo, W) clusters have clawlike structures, which have electrophilic metal sites to receive the approaching H 2 S molecule. After several hydrogen-atom transfer (HAT) processes, the final MS 4 •H 2 (IM-4) complexes are formed, which could desorb H 2 at a relatively low temperature. The singlet product MS 4 clusters contain the singlet S 2 moiety, similar to the adsorbed singlet S 2 on the surface of sulfide catalysts. The theoretical results are compared with the experiments of heterogeneous catalytic decomposition of H 2 S by MoS 2 catalysts. Our work may provide some insights into the optimal design of the relevant catalysts.

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Reductive Activation of Small Molecules by Anionic Coinage Metal Atoms and Clusters in the Gas Phase

Cited by 10 publications

References 72 publications

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

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

Ion spectroscopy in methane activation

Exploring the Reaction Mechanism of H₂S Decomposition with MS₃ (M = Mo, W) Clusters

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Reductive Activation of Small Molecules by Anionic Coinage Metal Atoms and Clusters in the Gas Phase

Cited by 10 publications

References 72 publications

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

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

Ion spectroscopy in methane activation

Exploring the Reaction Mechanism of H2S Decomposition with MS3 (M = Mo, W) Clusters

Contact Info

Product

Resources

About

Exploring the Reaction Mechanism of H₂S Decomposition with MS₃ (M = Mo, W) Clusters