Article
Chemistry, Multidisciplinary
Maximilian Muhr, Raphael Buhler, Hao Liang, Jonas Gilch, Christian Jandl, Samia Kahlal, Jean-Yves Saillard, Christian Gemel, Roland A. Fischer
Summary: Treatment of [Ru(COD)(MeAllyl)(2)] and [Ru(COD)(COT)] with GaCp* under hydrogenolytic conditions leads to the formation of reactive intermediates capable of activating Si-H or C-H bonds. The structures and properties of the resulting complex compounds [Ru(GaCp*)(3)(SiEt3)H-3] (1) and [Ru(GaCp*)(3)(C7H7)H-3] (2) have been investigated and characterized.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Yuan Yang, Ya-Ke Li, Yan-Xia Zhao, Gong-Ping Wei, Yi Ren, Knut R. Asmis, Sheng-Gui He
Summary: The study identifies a promising active species for dry (CO2) reforming of methane to syngas, and emphasizes the importance of temperature control over elementary steps in practical catalysis. This may significantly alleviate the carbon deposition originating from the pyrolysis of methane.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Damien Mahaut, Aurelien Chardon, Loic Mineur, Guillaume Berionni, Benoit Champagne
Summary: The article demonstrates the activation of methane using 1-aza-9-boratriptycene as an intramolecular frustrated Lewis pair (FLP) through density functional theory (DFT) analysis. The study shows that the nature of the Lewis base influences the selectivity over the reaction pathway, with N Lewis bases favoring the deprotonation mechanism and P bases the hydride abstraction one.
Article
Chemistry, Physical
Gong-Ping Wei, Qing-Yu Liu, Yan-Xia Zhao, Sheng-Gui He
Summary: In this study, the reactivity of Fe-O• radicals in iron-vanadium bimetallic oxide clusters were experimentally characterized. The rate constants for hydrogen abstraction from C-2-C-4 alkanes were found to be four orders of magnitude slower than the counterparts with Sc-O• radicals. Theoretical analysis showed that the rearrangements of electronic and geometric structures modulate the activity of Fe-O• radicals.
Review
Chemistry, Multidisciplinary
Yuan Yang, Yan-Xia Zhao, Sheng-Gui He
Summary: This review introduces gas phase ion-catalyzed methane conversion and discusses the direct coupling of methane molecules, the conversion of methane with oxidants such as O-2, O-3, and N2O, as well as the conversion of methane with CO2 and H2O. The obtained mechanistic insights may provide new clues for designing catalysts with better performance in methane conversion.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Wang Jiang, Xiuxiu Yang, Lin Lin, Chaoguo Yan, Yue Zhao, Minyan Wang, Zhuangzhi Shi
Summary: Metal-catalyzed C-H activation strategies provide an efficient approach for synthesis. In this study, visible-light-induced late-stage C-H activation was achieved using a single rhodium complex. The reaction offers advantages such as environmental friendliness and the utilization of inherent directing groups, providing a new platform for ligand design and preparation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jorge Juan Cabrera-Trujillo, Israel Fernandez
Summary: By means of Density Functional Theory calculations, the poorly understood factors controlling the complete meta-selectivity observed in the C-H activation reactions of alkylarenes promoted by aluminyl anions have been explored. It was found that the selectivity occurs during the initial nucleophilic addition step, where the key LP(Al)->pi*(C=C) molecular orbital interaction is more stabilizing for the meta-pathway.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Ya-Ke Li, Fabian Mueller, Wieland Schoellkopf, Knut R. Asmis, Joachim Sauer
Summary: The gas-phase reaction of NiAl2O4+ with CH4 was studied using mass spectrometry, vibrational action spectroscopy, and density functional theory (DFT). The results showed that methane can react to form either a methyl radical or formaldehyde through different pathways. The study also confirmed the proposed mechanism by experimental vibrational spectroscopy.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Ningjing Luo, Zhufeng Hou, Guo-Liang Chai
Summary: This study systematically explores the catalytic activity of tungsten monocarbide (WC) by studying the methane dehydrogenation and C-C coupling processes on WC surfaces using density functional theory (DFT) calculations. The results indicate that the W-terminated WC(0001) surface is the most favorable exposed surface with a lower surface energy. Additionally, the Co(111), Ni(111), and W-terminated WC(0001) surfaces exhibit similar catalytic properties in methane dehydrogenation, and the rate-limiting step on the W-terminated WC(0001) surface is the dissociation of CH*. C-C coupling through CH* intermediates on the W-terminated WC(0001) surface favors the formation of C2H2 kinetically.
APPLIED SURFACE SCIENCE
(2022)
Article
Biochemistry & Molecular Biology
Min Gao, Yong-Qi Ding, Jia-Bi Ma
Summary: This study reports on the N-2 adsorption on well-defined Y2C4H0,1- cluster anions under mild conditions. The results show that N-2 adsorption on Y2C4H- clusters is 50 times more reactive than on Y2C4- clusters. Further analysis reveals the important role of the H atom in modifying the charge distribution and facilitating the approach of N-2 to Y2C4H-.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2022)
Article
Chemistry, Physical
Xiaoqing Liu, Xue Li, Xiaoqian Yao, Weizhen Zhao, Lei Liu
Summary: The study demonstrates that ILs favor the H-H cleavage elemental step and the effects are more pronounced on intra-molecular FLPs compared to inter-molecular FLPs.
Article
Chemistry, Physical
Tatsuya Yamasaki, Atsushi Nishida, Nobuya Suganuma, Yang Song, Xiaohong Li, Junichi Murakami, Tetsuya Kodaira, Kyoko K. Bando, Tatsumi Ishihara, Tetsuya Shishido, Atsushi Takagaki
Summary: This study demonstrated the conversion of methane to hydrogen cyanide at low temperatures using NO and a Pt/Al2O3 catalyst, yielding higher HCN production rates and stability compared to traditional methods. In situ X-ray absorption fine structure analyses indicated that specific adsorbates on the catalyst were temperature-dependent and the presence of Pt-CN species correlated with the material's reactivity.
Article
Chemistry, Applied
Mai Yanagawa, Shingo Harada, Shumpei Hirose, Tetsuhiro Nemoto
Summary: The study developed a rhodium-catalyzed C-H functionalization reaction for synthesizing 2,3-fused indole variants using an alpha,beta-unsaturated enone as a directing group and electrophile. This annulation enabled the rapid assembly of valuable hydrocarbazolones from readily available indoles, and computational investigations were conducted to elucidate the reaction pathway and site-selectivity.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Md Emdadul Hoque, Ranjana Bisht, Anju Unnikrishnan, Sayan Dey, Mirja Md Mahamudul Hassan, Saikat Guria, Rama Nand Rai, Raghavan B. Sunoj, Buddhadeb Chattopadhyay
Summary: A method of para-selective borylation of aromatic amides is described using a newly designed ligand framework (defa), which shows excellent selectivity and reactivity for the para position. This method can contribute to the development of new catalytic systems and the synthesis of para-functionalized compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Applied
Xavier Marset, Marti Recort-Fornals, Malkaye Kpante, Adam Zielinski, Christopher Golz, Lawrence M. Wolf, Manuel Alcarazo
Summary: A series of strong it-acceptor polyfluorinated and dicationic chelating phosphines were synthesized and evaluated in the Rh-catalysed dimerization of norbornadiene, leading to the selective formation of specific products and site-selective arylation reactions. Theoretical calculations were performed to understand the origin of the observed regioselectivity.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Physics, Atomic, Molecular & Chemical
Aristeidis Baloglou, Marco Pritzi, Tobias F. Pascher, Jessica C. Hartmann, Marie-Luise Grutza, Milan Oncak, Philipp Kurz, Martin K. Beyer
Summary: The gas phase proton transfer reactivity of dianionic molybdenum oxysulfide clusters [Mo2O2S6](2-)and [Mo2O2S5](2-) was investigated in binary collisions, revealing Coulomb explosion phenomena with acids of increasing proton affinity. Quantum chemical calculations predicted significantly higher proton affinities for the clusters compared to other acids, and reaction potential energy surfaces explained the observed phenomena. A Coulomb barrier was present between the collision complex and products, varying in position across different acids.
INTERNATIONAL JOURNAL OF MASS SPECTROMETRY
(2021)
Article
Chemistry, Physical
Joao Ameixa, Eugene Arthur-Baidoo, Joao Pereira-da-Silva, Julio C. Ruivo, Marcio T. do N. Varella, Martin K. Beyer, Milan Oncak, Filipe Ferreira da Silva, Stephan Denifl
Summary: This study examines the electron attachment properties of simple derivatives in biochemical pathways and reveals significant differences in dissociative electron attachment reactions between two molecules.
Article
Chemistry, Physical
Jakob Heller, Ethan M. Cunningham, Christian van der Linde, Milan Oncak, Martin K. Beyer
Summary: Controlled activation of water molecules is crucial for efficient water splitting, as shown by studying the insertion reaction of hydrated singly charged manganese ions using IRMPD and mass spectrometry techniques. Comparison of IRMPD spectra and quantum chemical calculations reveal that the inserted structure requires stabilization through hydration.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Physical
Shan Jin, Jakob Heller, Christian van der Linde, Milan Oncak, Martin K. Beyer
Summary: The iron hydride molecular cation FeH+ is believed to exist in the interstellar medium, but has not been identified in observations. In this study, infrared spectroscopy was used to investigate the ro-vibrational lines of FeH+ tagged with two argon atoms. The results show that the molecule has specific symmetry and exhibits thermal broadening and redshift at the experimental temperature.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Biochemical Research Methods
Marco Pritzi, Tobias F. Pascher, Marie-Luise Grutza, Philipp Kurz, Milan Oncak, Martin K. Beyer
Summary: Molybdenum sulfides are a promising and inexpensive substitute for platinum catalysts. Through gas-phase experiments, we find that the dissociation pathways of halogenated molybdenum sulfides are drastically different from pure molybdenum sulfides, highlighting possible reaction pathways in a catalytic environment.
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
(2022)
Article
Chemistry, Multidisciplinary
Milan Oncak, Chi-Kit Siu, Christian van der Linde, Wai Kit Tang, Martin K. Beyer
Summary: The molecular processes behind hydrogen evolution reactions are complex and difficult to understand in macroscopic electrochemical cells. Gas phase models, consisting of metal ions and a small number of water molecules, provide unique opportunities to study the reaction pathways in detail. The mechanisms for hydrogen evolution on the ground state and excited state potential energy surfaces have been analyzed and compared, identifying and characterizing five distinct mechanisms for the evolution of atomic or molecular hydrogen.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Magdalena Salzburger, Milan Oncak, Christian van Der Linde, Martin K. Beyer
Summary: This study investigates the temperature-dependent blackbody infrared radiative dissociation (BIRD) of CO3·-(H2O)1,2 to determine water binding energies and assess the influence of multiple isomers on dissociation kinetics. The results show that the multiple-well MEM approach yields superior results in systems with several low-lying minima.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Maximilian G. Muenst, Erik Barwa, Martin K. Beyer
Summary: Proton transfer reaction mass spectrometry has untapped potential for analyzing high-purity process and inert gases. This study investigated the gas-phase reactions and kinetics of low-proton affinity precursor ions, such as ArH+ and N2H+, with acetone. The dominant product ion was protonated acetone, but ArH+ produced a higher abundance of fragment ions compared to N2H+.
Article
Chemistry, Multidisciplinary
Maximilian G. Muenst, Erik Barwa, Milan Oncak, Martin K. Beyer
Summary: Proton transfer reactions are essential for chemical ionization, particularly in trace gas analysis in air. This study focused on the PTR of N2H+ and ArH+ with various reaction gases, including O-2, N-2, CH4, CO2, NO2, H2O, and CH3OH, with the goal of expanding their application to high-purity inert gas analysis. The reaction pathways and energetics were determined through quantum chemical calculations, and it was found that most reactions occur at or near collision rate. Understanding the fragmentation pathways and branching ratios is crucial for identifying and quantifying trace compounds in highly exothermic proton transfer reactions.
ISRAEL JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Physical
Magdalena Salzburger, Rizalina T. Saragi, Frank J. Wensink, Ethan M. Cunningham, Martin K. Beyer, Joost M. Bakker, Milan Oncak, Christian van der Linde
Summary: Transition metals, such as niobium, play a crucial role in industrial applications like catalysis. In this study, the activation of CO2 and H2O by [NbO3]- in the gas phase was investigated using infrared spectroscopy and theoretical calculations. By combining Fourier-transform ion cyclotron resonance mass spectrometry with tunable IR laser light, spectra of various species including [NbO3]-, [NbO2(OH)2]-, [NbO2(OH)2]-(H2O), and [NbO(OH)2(CO3)]- were obtained. The results confirmed that [NbO3]- can react with water to form [NbO2(OH)2]- without any energy barrier, and subsequent reaction with CO2 leads to the formation of [NbO(OH)2(CO3)]- with a [CO3] moiety.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Biochemical Research Methods
Christian van der Linde, Milan Oncak, Ethan M. Cunningham, Wai Kit Tang, Chi-Kit Siu, Martin K. Beyer
Summary: This article discusses spectroscopic probes and quantum chemistry as means of investigating the structure of gas-phase hydrated ions. The H/D exchange is also used for structure elucidation. Nanocalorimetry is employed to search for thermochemical signatures that differentiate surface solvation from internal solvation. Examples of size-dependent reactivity are reviewed to demonstrate the influence of solvation on cluster rearrangements and ion-molecule reactions.
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
(2023)
Article
Instruments & Instrumentation
Leander Haug, Christoph Griesser, Christoph W. Thurner, Daniel Winkler, Toni Moser, Marco Thaler, Pit Bartl, Manuel Rainer, Engelbert Portenkirchner, David Schumacher, Karsten Dierschke, Norbert Koepfle, Simon Penner, Martin K. Beyer, Thomas Loerting, Julia Kunze-Liebhaeuser, Bernhard Kloetzer
Summary: This paper presents a versatile laboratory-based near ambient pressure X-ray photoelectron spectroscopy (XPS) instrument, which is highly customized with geometry, exchangeable manipulators, and sample stages for various electrochemical and catalytic experiments. The instrument provides access to a broad choice of functional materials and their specific surface processes. The combination of manipulators allows for experiments in solid state/gas phase interactions, liquid electrochemistry, and cryogenic experiments for ice-like materials, making it a flexible and modular system for in situ and operando XPS experiments.
REVIEW OF SCIENTIFIC INSTRUMENTS
(2023)
Article
Chemistry, Physical
Marco Pritzi, Tobias F. Pascher, Marie-Luise Grutza, Philipp Kurz, Milan Oncak, Martin K. Beyer
Summary: Molybdenum sulfides and molybdenum oxysulfides are potential and cost-effective alternatives to platinum catalysts for hydrogen evolution reaction (HER). Through collision induced dissociation experiments, stable species [Mo2O2S4]- and [HMo2O2S4]- with potential HER activity are identified.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Jakob Heller, Ethan M. Cunningham, Jessica C. Hartmann, Christian van der Linde, Milan Oncak, Martin K. Beyer
Summary: In this study, infrared multiple photon dissociation spectroscopy was used to investigate the hydrated vanadium cation. The results revealed the fragmentation channels and spectral patterns of the cation at different cluster sizes, providing insights into the structural and chemical changes of the hydrated vanadium cation.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Jakob Heller, Tobias F. Pascher, Dominik Muss, Christian van der Linde, Martin K. Beyer, Milan Oncak
Summary: Photochemical hydrogen evolution provides promising prospects for light harvesting. Hydrated monovalent vanadium ions with varying hydration shell sizes were studied using photodissociation spectroscopy. The competition between water loss and hydrogen evolution was observed in the clusters, with electronic transitions modeled using multireference methods for smaller clusters.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
