Das Gorachand, Prabhudesai Vaibhav S, Sajeev Y
Department of Nuclear and Atomic Physics, Tata Institute of Fundamental Research, Mumbai, India.
Theoretical Chemistry Section, Bhabha Atomic Research Centre, Mumbai, India.
Commun Chem. 2025 May 13;8(1):145. doi: 10.1038/s42004-025-01543-w.
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 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.
通过直接且共振地将低能量自由电子捕获到其σ轨道中来化学活化化学键，从概念上讲很简单，但却是实现特定状态和特定键的化学控制最具吸引力的可能性。然而，由于电子进入σ轨道的共振电子捕获截面非常低，这种直接方法尚未得到实验探索。在此，我们报告了通过将低能量电子直接捕获到σ轨道而实现的键选择性脱官能化和脱氢反应。这些反应的显著效率可归因于σ轨道与其相邻或共轭轨道的叠加。分子中这种量子叠加的普遍存在为利用低能量自由电子控制化学反应的愿望开辟了前所未有的实验可能性。
