期刊
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
卷 24, 期 35, 页码 20721-20727出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/d2cp02733j
关键词
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资金
- American Chemical Society Petroleum Research Fund (ACS PRF) [60481-ND6]
Efficient activation and functionalization of the C-H bond under mild conditions are of great interest in chemical synthesis. This study investigates a previously proposed method and proposes a more favorable reaction pathway for C-H bond activation.
Efficient activation and functionalization of the C-H bond under mild conditions are of a great interest in chemical synthesis. We investigate the previously proposed spin-accelerated activation of the C(sp(2))-H bond by a Fe(ii)-based catalyst to clarify the role of the intermediate triplet state in the reaction mechanism. High-level electronic structure calculations on a small model of a catalytic system utilizing the coupled cluster with the single, double, and perturbative triple excitations [CCSD(T)] are used to select the density functional for the full-size model. Our analysis indicates that the previously proposed two-state quintet-singlet reaction pathway is unlikely to be efficient due to a very weak spin-orbit coupling between these two spin states. We propose a more favorable multi-state quintet-triplet-singlet reaction pathway and discuss the importance of the intermediate triplet state. This triplet state facilitates a spin-accelerated reaction mechanism by strongly coupling to both quintet and singlet states. Our calculations show that the C-H bond activation through the proposed quintet-triplet-singlet reaction pathway is more thermodynamically favorable than the single-state quintet and two-state singlet-quintet mechanisms.
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