ReB₆^-: A Metallaboron Analog of Metallabenzenes

Metallabenzenes are a class of molecules in which a CH unit in benzene is replaced by a functionalized transition-metal atom. While all-boron analogues of aromatic and antiaromatic hydrocarbons are well-known, there have not been any metallaboron analogs. We have produced and investigated two metal-doped boron clusters, ReB₆^- and AlB₆^-, using high-resolution photoelectron imaging and quantum chemical calculations. Vibrationally resolved photoelectron spectra have been obtained and compared with the theoretical results. The ReB₆^- cluster is found to be perfectly planar with a B-centered hexagonal structure (C₂, ¹A₁), while AlB₆^- is known to have a similar structure, but with a slightly out-of-plane distortion (C, ¹A'). Chemical bonding analyses show that the closed-shell ReB₆^- is doubly σ- and π-aromatic, while AlB₆^- is known to be σ-aromatic and π-antiaromatic. The out-of-plane distortion in AlB₆^- is due to antiaromaticity, akin to the out-of-plane distortion of the prototypical antiaromatic cyclooctatetraene. The π-bonding in ReB₆^- is compared with that in both benzene and rhenabenzene [(CO)₄ReC₅H₅], and remarkable similarities are found. Hence, ReB₆^- can be viewed as the first metallaboron analog of metallabenzenes and it may be viable for syntheses with suitable ligands.