DFT mechanistic studies of boron–silicon exchange reactions between silyl-substituted arenes and boron bromides
Literature Information
Christopher S. Qiu, Nicholas P. Qiu, Christopher Flinn, Yuming Zhao
C–B bond forming reactions are important methodologies in modern synthetic chemistry, since many borylated organic substrates, ranging from alkanes and alkenes to arenes and heteroarenes, are useful intermediates for the synthesis of natural products, pharmaceuticals, and organic π-conjugated materials. Among numerous borylation methods, C–Si/B–Br exchange reactions have attracted increasing attention in recent years. While experimental exploration has been continually carried out for more than two decades, mechanistic insights into this type of reaction have not yet been clearly established. To address this deficiency of knowledge, we performed density functional theory (DFT) calculations to map out the reaction pathways for a range of boron–silicon exchange reactions between boron tribromide (BBr3) and trimethylsilyl-substituted arenes (TMSAr). Our computational analyses have disclosed the energetic, structural, and electronic properties for key stationary points on the potential energy surfaces (PES) in both the gas and solution (CH2Cl2) phases.
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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.














