Abstract
Boron displays many unusual structural and bonding properties due to its electron deficiency. Here we show that a boron atom in a boron monoxide cluster (B9O−) exhibits transition-metal-like properties. Temperature-dependent photoelectron spectroscopy provided evidence of the existence of two isomers for B9O−: the main isomer has an adiabatic detachment energy (ADE) of 4.19 eV and a higher energy isomer with an ADE of 3.59 eV. The global minimum of B9O− is found surprisingly to be an umbrella-like structure (C6v, 1A1) and its simulated spectrum agrees well with that of the main isomer observed. A low-lying isomer (Cs, 1A′) consisting of a BO unit bonded to a disk-like B8 cluster agrees well with the 3.59 eV ADE species. The unexpected umbrella-like global minimum of B9O− can be viewed as a central boron atom coordinated by a η7-B7 ligand on one side and a BO ligand on the other side, [(η7-B7)-B-BO]−. The central B atom is found to share its valence electrons with the B7 unit to fulfill double aromaticity, similar to that in half-sandwich [(η7-B7)-Zn-CO]− or [(η7-B7)-Fe(CO)3]− transition-metal complexes. The ability of boron to form a half-sandwich complex with an aromatic ligand, a prototypical property of transition metals, brings out new metallomimetic properties of boron.
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