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 Biphenylene analogues in which one of the benzene rings has been replaced by a different (4n + 2) pi-electron system have so far been associated only with organic compounds(4,5).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.
