期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 -, 期 -, 页码 -出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.2c03835
关键词
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资金
- National Natural Science Foundation of China (NSFC) [21833011, 2021YFA1500200]
- National Key R&D Program of China [ISF 520/18]
- K. C. Wong Education Foundation
- Israel Science Foundation
- [21873103]
Valence-inverted reactivity (VIR) is discovered through high-level computations of excited states of Ni(II) complexes that are generated by triplet energy transfer, and it plays a significant role in C-H bond activation and cross-coupling reactions.
Valence-inverted reactivity (VIR) is discovered here through high-level computations of excited states of Ni(II) complexes that are generated by triplet energy transfer. For example, the so-generated 3[(Ar)(bpy)NiII(Br)] species possesses a valence-inverted occupancy, dxy1dxz1dx2-y22, wherein the upper-most dx2-y2 orbital is metal-ligand antibonding. This state promotes C-H bond activation of THF and its cross-coupling to the aryl ligand. Thus, due to the metal-ligand antibonding character of dx2-y2, the dxy1dx2-y22 subshell opens a Ni-coordination site by shifting the bidentate bipyridine ligand to monodentate plus a dangling pyridine. The tricoordinate Ni(II) intermediate inserts into a C-H bond of THF, transfers a proton to the dangling pyridine moiety, and eventually generates an arylated THF by reductive-coupling. The calculated high kinetic isotope effect is in accord with experiment, both revealing C-H activation. The VIR pattern is novel, its cross-coupling reaction is highly useful, and it is generally expected to occur in other d8 complexes.
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