Labile ligands on some Lewis super acids: a computational study
文献情報
Paola Nava, Yannick Carissan, Stéphane Humbel
Lewis super-acids, like Sn(OTf)4 or In(OTf)3, OTf = CF3SO3−, are efficient catalysts for cycloisomerization reactions. We report here a study on the coordination of ligands (or of solvent molecules) around such catalysts at density functional theory level. Using the Sn-based compound as an example, we consider the interaction with several molecules, usually nearby in reaction conditions. These include nitromethane, esters and diesters, dimethylsulfoxide, and so on. We establish a ladder of interaction strengths and show that dimethylsulfoxyde molecules can displace triflate ligands from the metallic center. This leads to the main conclusions that solvent molecules directly coordinate Sn centers and that non-coordinating triflates are potentially free in solution despite their anionic characteristic.
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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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