Insight into the relative reactivity of “Frustrated Lewis pairs” and stable carbenes in activating H2 and CH4: A comparative computational study

Literature Information

Publication Date 2010-03-29
DOI 10.1039/B924586C
Impact Factor 3.676
Authors

Haixia Li, Lili Zhao, Gang Lu, Yirong Mo, Zhi-Xiang Wang


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Abstract

Computational study has been conducted to gain insight into the relative reactivity of stable carbenes (1 and 2) and typical frustrated Lewis pairs (FLPs, 3–6) in activating H2 and CH4. For the FLP H2 activations, despite the quite different basicities of the Lewis base components, they have comparable reactivities. The unexpected relative reactivity can be attributed to the following two factors: (i) the vacant carbene C: pπ orbital, which is important when carbene works alone but does not participate in the FLP activation; and (ii) the electrostatic interaction between the Lewis base center and the approaching H atom which plays an important role and can either favor or disfavor a reaction. These explanations are also applicable to methane activations. The study brings two messages to the experimentalists for constructing FLPs: (i) it is recommended to use P- and N-centered Lewis bases to construct FLPs for H2 activation because using more reactive components does not benefit the activation; and (ii) the FLPs are less reactive in activating CH4 than H2. In addition, using more reactive carbenes as Lewis bases in FLPs does not necessarily benefit the methane activation.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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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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