期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 139, 期 44, 页码 15564-15567出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.7b06086
关键词
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资金
- National Natural Science Foundation of China (NSFC) [21473215, 21290194, 21521062]
- Institute of Chemistry, Chinese Academy of Sciences
Iron-catalyzed alkene [2+2] cycloaddition reactions represent a promising stepwise pathway to effect the kinetically hindered concerted [2+2] cycloaddition. However, the fundamental reactivity paradigm of these reactions remains unclear. Based on high level combined CASPT2/DFT modelings, herein we reveal an unprecedented substrate-dependent two-state reactivity scenario for the key C-C coupling in this iron catalysis, in which the representative substrates of mono-olefins only and mono-olefin plus 1,3-diene exhibit different reactivity paradigms. The role of the redox-active ligand is found to generate a ferric oxidation state for the metallacyclic intermediate of C-C coupling, thereby rendering a thermodynamically more accessible Fem/Fei reductive elimination process compared with the otherwise Fe-II/ Fe-0 one. The enhancement of the spin state transition efficiency between the singlet and triplet states is predicted as an alternative way to increase the C-C coupling reactivity in the cross [2+2] cycloaddition reactions between mono-olefins and dienes. This work highlights the ab initio multi-reference 'method in describing 'very complicated open-shell iron catalysis..
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