Heavy-Atom Tunneling in Ring-Closure Reactions of Beryllium Ozonide Complexes,Journal of the American Chemical Society

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Heavy-Atom Tunneling in Ring-Closure Reactions of Beryllium Ozonide Complexes
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2024-09-18 , DOI: 10.1021/jacs.4c06137
Yangyu Zhou ₁ , Wenbin Fan ₁ , Jingjing Tang ₁ , Wei Fang ₁ , Mingfei Zhou ₁

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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.

中文翻译：

臭氧化铍配合物闭环反应中的重原子隧道效应

长期以来，量子力学隧道效应（QMT）一直被认为对于理解化学反应机制至关重要，特别是在涉及氢等轻原子的反应中。然而，最近的发现扩大了这种理解，将重原子隧道反应包括在内。在本报告中，我们观察了两个重原子隧道反应，涉及从端接键合臭氧化物络合物 OBeOOO ( A ) 和 BeOBeOOO ( C ) 自发转化为其相应的侧接臭氧化物异构体 OBe(分别在低温氖基体中的 η ² -O ₃ ) ( B ) 和 BeOBe(η ² -O ₃ ) ( D )。这一发现得到了速率常数的弱温度依赖性和异常大的¹⁶ O/ ¹⁸ O 动力学同位素效应的支持。量子化学计算表明两种闭环反应的势垒极低 (<1 kcal/mol)。此外，对这两个反应的瞬时理论计算表明，隧道过程涉及所有四个氧原子的协同运动。

更新日期：2024-09-18

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