Aromaticity-promoted CS2 activation by heterocycle-bridged P/N-FLPs: a comparative DFT study with CO2 capture
文献情報
Yuanyuan Li, Danling Zhuang, Rulin Qiu, Jun Zhu
Carbon dioxide (CO2) capture has attracted considerable attention from both experimental and theoretical chemists. In comparison, carbon disulfide (CS2) activation is less developed. Here, we carry out a thorough comparative density functional theory study to examine the reaction mechanisms of CS2 activation by five-membered heterocycle-bridged P/N frustrated Lewis pairs (FLPs). Calculations suggest that despite a weaker carbon–sulfur bond, all the CS2 activations have higher reaction barriers than the CO2 capture, which could be attributed to electrostatic repulsion between FLPs and CS2 caused by the reversed polarity of CS in CS2 rather than the electrostatic attraction in CO2 capture. In addition, aromaticity is found to play an important role in CS2 capture as it stabilizes both the transition states and products in heterocycle-bridged FLPs. All these findings could be useful for experimentalists to realize small molecule activations by FLPs.
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掲載誌
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.














