期刊
NATURE
卷 578, 期 7796, 页码 563-+出版社
NATURE PORTFOLIO
DOI: 10.1038/s41586-020-2004-7
关键词
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资金
- US Department of Energy (DOE) through the Los Alamos National Laboratory (LANL) Laboratory Directed Research and Development Program
- LANL G. T. Seaborg Institute for Transactinium Science
- Office of Workforce Development for Teachers and Scientists, Office of Science Graduate Student Research (SCGSR) program (GRA Fellowship)
- Office of Basic Energy Sciences, Heavy Element Chemistry program
- Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences of the US DOE [USDOE/DESC002183]
- US National Science Foundation [CHE-1265608, CHE-1565658]
- DOE [DE-AC05-06OR23100]
- National Nuclear Security Administration of the US DOE [DE-AC52-06NA25396]
Aromaticity and antiaromaticity, as defined by Huckel's rule, are key ideas in organic chemistry, and are both exemplified in biphenylene(1-3)-a molecule that consists of two benzene rings joined by a four-membered ring at its core. Biphenylene analogues in which one of the benzene rings has been replaced by a different (4n + 2) pi-electron system have so far been associated only with organic compounds(4,5). In addition, efforts to prepare a zirconabiphenylene compound resulted in the isolation of a bis(alkyne) zirconocene complex instead(6). Here we report the synthesis and characterization of, to our knowledge, the first 2-metallabiphenylene compounds. Single-crystal X-ray diffraction studies reveal that these complexes have nearly planar, 11-membered metallatricycles with metrical parameters that compare well with those reported for biphenylene. Nuclear magnetic resonance spectroscopy, in addition to nucleus-independent chemical shift calculations, provides evidence that these complexes contain an antiaromatic cyclobutadiene ring and an aromatic benzene ring. Furthermore, spectroscopic evidence, Kohn-Sham molecular orbital compositions and natural bond orbital calculations suggest covalency and delocalization of the uranium f(2) electrons with the carbon-containing ligand. The synthesis of uranium- and thorium-containing metallabiphenylenes demonstrates the ability of the actinides to stabilize aromatic/antiaromatic structures where transition metals have failed.
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