A gas-phase kinetic study of the silylene addition reaction SiH2 + C2D4 as a function of temperature and pressure: isotope effects and mechanistic complexities
文献信息
N. Al-Rubaiey, R. Becerra, R. Walsh
Time-resolved studies of silylene, SiH2, generated by laser flash photolysis of phenylsilane, have been carried out to obtain rate constants for its bimolecular reaction with C2D4. The reaction was studied in the gas phase, over the pressure range 1–100 Torr (in SF6 bath gas) at five temperatures in the range 291–595 K. The reaction of SiH2 + C2D4 was pressure dependent but significantly less so than that of SiH2 + C2H4 studied earlier. The high pressure limiting rate constants were the same for the two reaction systems within experimental error. RRKM modelling studies were carried out but the calculated inverse isotope effects, kD/kH, were poorly reproduced by a mechanism consisting of a simple third body assisted association reaction. When this was extended to include a reversible isotopic scrambling process, the RRKM modelling of the isotope effects gave better agreement with experiment, although not perfect agreement with the pressure dependence. This mechanism, involving the reversible isomerisation of silirane-d4 to ethylsilylene-d4, is consistent with thermochemical and ab initio calculations of the energy surface.
期刊推荐

Journal of Medicinal Chemistry

Planta Medica

Pure and Applied Chemistry

Science Progress

Organic Preparations and Procedures International

Science

Molecular Pharmacology

Proceedings of the National Academy of Sciences of the United States of America

Russian Chemical Reviews

European Journal of Wood and Wood Products
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.




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