复旦大学周鸣飞团队报道了铍Ozonide配合物闭环反应中的重原子隧穿。相关研究成果于2024年9月18日发表于国际顶尖学术期刊《美国化学会杂志》。

量子力学隧穿（QMT）长期以来一直被认为是理解化学反应机制的关键，特别是在涉及氢等轻原子的反应中。然而，最近的发现将这一理解扩展到包括重原子隧穿反应。

该文中，研究人员观察了两个重原子隧穿反应，涉及在低温氖基质中从末端键合的铍臭氧化物络合物OBeOOO（A）和BeOBeOOO。量子化学计算揭示了两种闭环反应的极低势垒（<1 kcal/mol）。此外，对这两种反应的瞬子理论计算揭示，隧穿过程涉及所有四个氧原子的协同运动。

附：英文原文

Title: Heavy-Atom Tunneling in Ring-Closure Reactions of Beryllium Ozonide Complexes

Author: Yangyu Zhou, Wenbin Fan, Jingjing Tang, Wei Fang, Mingfei Zhou

Issue&Volume: September 18, 2024

Abstract: Quantum mechanical tunneling (QMT) has long been recognized as crucial for understanding chemical reaction mechanisms, particularly in reactions involving light atoms like hydrogen. However, recent findings have expanded this understanding to include heavy-atom tunneling reactions. In this report, we present the observation of two heavy-atom tunneling reactions involving the spontaneous conversions from end-on bonded beryllium ozonide complexes, OBeOOO (A) and BeOBeOOO (C), to their corresponding side-on bonded ozonide isomers, OBe(η2-O3) (B) and BeOBe(η2-O3) (D), respectively, in a cryogenic neon matrix. This discovery is supported by the weak temperature dependence of the rate constants and unusually large 16O/18O kinetic isotope effects. Quantum chemistry calculations reveal extremely low barriers (<1 kcal/mol) for both ring-closure reactions. Additionally, instanton theory calculations on both reactions unveil that the tunneling processes involve the concerted motion of all four oxygen atoms.

DOI: 10.1021/jacs.4c06137

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c06137