期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 144, 期 22, 页码 9853-9858出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.2c02581
关键词
-
资金
- National Science Foundation [CHE-2103696]
In this study, we synthesized a formal Cu(III) metallacyclopentadiene dimer by incorporating bulky groups, and successfully obtained a special cyclobutadiene through reductive elimination.
Despite the widespread use of copper catalysis for the formation of C-C bonds, debate about the mechanism persists. Reductive elimination from Cu(III) is often invoked as a key step, yet examples of its direct observation from isolable complexes remain limited to only a few examples. Here, we demonstrate that incorporation of bulky mesityl (Mes) groups into the alpha-positions of a phenanthrene-appended zirconacyclopentadiene, Cp2Zr(2,5-Mes(2)-phenanthro[9,10]C-4), enables efficient oxidative transmetalation to the corresponding, formal Cu(III) metallacyclopentadiene dimer. The dimer was quantitatively converted to a structurally analogous anionic monomer [(Bu4N)-Bu-n]-{Cl2Cu(2,5-Mes(2)-phenanthro[9,10]C-4)} upon treatment with [(Bu4N)-Bu-n][Cl]. Both metallacycles undergo quantitative reductive elimination upon heating to generate phenanthrocyclobutadiene and a Cu(I) species. Due to the steric protection provided by the mesityl groups, this cyclobutadiene was isolated and thoroughly characterized to reveal antiaromaticity comparable to that of free cyclobutadiene, which imbues it with a small highest occupied molecular orbital-lowest unoccupied molecular orbital energy gap of 1.85 eV and accessible reduced and oxidized electronic states.
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