Actinide 2-metallabiphenylenes that satisfy Hückel’s rule

Justin K. Pagano, Jing Xie, Karla A. Erickson, Stephen K. Cope, Brian L. Scott, Ruilian Wu, Rory Waterman, David E. Morris (), Ping Yang (), Laura Gagliardi () and Jaqueline L. Kiplinger ()
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Justin K. Pagano: Los Alamos National Laboratory
Jing Xie: University of Minnesota
Karla A. Erickson: Los Alamos National Laboratory
Stephen K. Cope: Los Alamos National Laboratory
Brian L. Scott: Los Alamos National Laboratory
Ruilian Wu: Los Alamos National Laboratory
Rory Waterman: University of Vermont
David E. Morris: Los Alamos National Laboratory
Ping Yang: Los Alamos National Laboratory
Laura Gagliardi: University of Minnesota
Jaqueline L. Kiplinger: Los Alamos National Laboratory

Nature, 2020, vol. 578, issue 7796, 563-567

Abstract: Abstract Aromaticity and antiaromaticity, as defined by Hückel’s rule, are key ideas in organic chemistry, and are both exemplified in biphenylene1–3—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 Biphenylene analogues in which one of the benzene rings has been replaced by a different (4n + 2) π-electron system have so far been associated only with organic compounds4,5. In addition, efforts to prepare a zirconabiphenylene compound resulted in the isolation of a bis(alkyne) zirconocene complex instead6. 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 f2 electrons with the carbon-containing ligand.

Date: 2020
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DOI: 10.1038/s41586-020-2004-7

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