Direct capture of a low-energy free-electron into delocalized σ^* orbitals for enabling state- and bond-selective reactions

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2025年5月13日

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Gorachand Das,
Vaibhav S. Prabhudesai,
Y. Sajeev

摘要

Chemically activating a bond by capturing a low-energy free-electron directly and resonantly into its σ^* orbital is conceptually simple and yet the most fascinating possibility for achieving state-specific and bond-specific chemical control. But this direct approach has not been explored experimentally due to the very low resonant electron capture cross-section of electrons into the σ^* orbital. Here we report defunctionalization and dehydrogenation reactions that are bond-selectively enabled by the direct capture of a low-energy electron into the σ^* orbital. The remarkable efficiency of these reactions can be attributed to superpositions of the σ^* orbital with its vicinal or conjugated ${\sigma }_{{{{\rm{CH}}}}}^{* }$ $σ_{CH}^{*}$ orbitals. The ubiquity of such quantum superpositions in molecules opens unprecedented experimental possibilities in the aspiration to control chemical reactions using low-energy free-electrons.

Direct capture of a low-energy free-electron into delocalized σ* orbitals for enabling state- and bond-selective reactions

摘要

Direct capture of a low-energy free-electron into delocalized σ^* orbitals for enabling state- and bond-selective reactions