American Chemical Society
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Spectroscopic and Theoretical Insights into H2 Activation on Uranium Monoxide: Homolytic H2 Cleavage Mediated by Intermediate OU(η2‑H2)

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journal contribution
posted on 2024-07-10, 21:29 authored by Zhen Pu, Xiaoguo Fu, Jianwei Qin, Hu Yang, Maobing Shuai, Fang Li
Elucidating molecular-level interactions between dihydrogen (H2) and uranium oxides reveals fundamental insights into the intrinsic H2 activation mechanisms underlying processes such as heterogeneous catalysis over uranium oxides and corrosion of uranium induced by H2. Herein, the reactions of H2 with uranium monoxide (UO) molecules have been investigated via a combination of matrix-isolation infrared spectroscopy and quantum chemical calculations. A side-on bonded H2 complex, OU­(η2-H2), is identified at 3733.7 and 800.3 cm–1. This species is regarded as a crucial intermediate along H2 activation pathways. Bonding analysis reveals cooperative U­(π5f/6d) → H2(σ*) π// backdonation and U ← H2(σ) σ donation in OU­(η2-H2) that facilitate the activation of the H2 moiety. Upon λ > 550 nm photoirradiation, OU­(η2-H2) isomerizes into H2UO, indicating the homolytic H2 cleavage on UO. Mechanistic details of H2 adsorption and dissociation on UO molecules have been further elucidated.