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

Chemically activating a bond by capturing a low-energy free-electron directly and resonantly into its sigma* 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 sigma* orbital. Here we report defunctionalization and dehydrogenation reactions that are bond-selectively enabled by the direct capture of a low-energy electron into the sigma* orbital. The remarkable efficiency of these reactions can be attributed to superpositions of the sigma* orbital with its vicinal or conjugated sigma CH*\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$${\sigma }_{{{{\rm{CH}}}}}<^>{* }$$\end{document} 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.