Partially-ligated anionic ruthenium carbonyl clusters react with alkenes, arenes, and alkanes in the gas phase; the products undergo extensive C-H activation and lose dihydrogen and carbon monoxide under collision-induced dissociation conditions. Triethylsilane and phenylsilane are also reactive towards the unsaturated clusters, and oxygen was shown to rapidly break down the cluster core by oxidative cleavage of the metal-metal bonds. These qualitative gas-phase reactivity studies were conducted using an easily-installed and inexpensive modification of a commercial electrospray ionization mass spectrometer. Interpretation of the large amounts of data generated in these studies is made relatively straightforward by employing energy-dependent electrospray ionization mass spectrometry (EDESI-MS).
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http://dx.doi.org/10.1016/j.jasms.2008.12.006 | DOI Listing |
J Chem Theory Comput
January 2025
Laboratoire ICB, UMR-6303 CNRS/uB, Université de Bourgogne, 9 avenue Alain Savary, 21078 Cedex Dijon, France.
We report full quantum-computed average microcanonical, initial state-specific, and canonical cumulative time-delays associated with the O + O scattering, presented as a function of total energy (in relation to an idealized molecular beam experiment) or temperature (for the properties of the gas phase in bulk conditions). We show that these quantities are well-defined and computable, with a temperature-dependent (canonical) time-delay presenting a smooth, monotonic decreasing behavior with temperature, despite an energy-dependent (microcanonical) time-delay of apparent chaotic character. We discuss differences in behavior when considering isotopic variations, O + OO and O + OO, with respect to the reference process O + OO and reveal a greater magnitude of the cumulative time-delay when genuinely reactive events can take place, in the presence of O.
View Article and Find Full Text PDFChem Sci
January 2025
Molecular Horizons and School of Chemistry and Molecular Bioscience, University of Wollongong Wollongong New South Wales 2522 Australia
Although electrostatic catalysis can enhance the kinetics and selectivity of reactions to produce greener synthetic processes, the highly directional nature of electrostatic interactions has limited widespread application. In this study, the influence of oriented electric fields (OEF) on radical addition and atom abstraction reactions are systematically explored with ion-trap mass spectrometry using structurally diverse distonic radical ions that maintain spatially separated charge and radical moieties. When installed on rigid molecular scaffolds, charged functional groups lock the magnitude and orientation of the internal electric field with respect to the radical site, creating an OEF which tunes the reactivity across the set of gas-phase carbon-centred radical reactions.
View Article and Find Full Text PDFAcc Chem Res
January 2025
Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
ConspectusReactions of gas phase molecules with surfaces play key roles in atmospheric and environmental chemistry. Reactive uptake coefficients (γ), the fraction of gas-surface collisions that yield a reaction, are used to quantify the kinetics in these heterogeneous and multiphase systems. Unlike rate coefficients for homogeneous gas- or liquid-phase reactions, uptake coefficients are system- and observation-dependent quantities that depend upon a multitude of underlying elementary steps.
View Article and Find Full Text PDFACS EST Air
September 2024
Office of the Director, Health Effects Laboratory Division, National Institute for Occupational Safety and Health, Morgantown, West Virginia 26505, United States.
During use of sodium hypochlorite bleach, gas-phase hypochlorous acid (HOCl) and chlorine (Cl) are released, which can react with organic compounds present in indoor air. Reactivity between HOCl/Cl and limonene, a common constituent of indoor air, has been observed. The purpose of this study was to characterize the chemical species generated from gas-phase reactions between HOCl/Cl and limonene.
View Article and Find Full Text PDFMaterials (Basel)
December 2024
Department of Biotechnology and Bioprocess Engineering, Faculty of Chemical and Process Engineering, Warsaw University of Technology, Waryńskiego 1, 00-645 Warsaw, Poland.
Cleaning of surfaces without complex cleaning agents is an important subject, especially in food, pharmaceutical, and biomedical applications. The subject of microbubble and nanobubble cleaning is considered one of the most promising ways to intensify this process. In this work, we check whether and how the purity of water used for microbubble generation, as well as the gas used, affects the effectiveness of cleaning stainless-steel surfaces.
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