Transition-metal-centered monocyclic boron wheels are important candidates in the family
of planar hypercoordinate species that show intriguing structure, stability and bonding
situation. Through the detailed potential energy surface explorations of MB9
− (M Fe, Ru,
Os) clusters, we introduce herein OsB9
− to be a new member in the transition-metalcentered
borometallic molecular wheel gallery. Previously, FeB9
− and RuB9
− clusters were
detected by photoelectron spectroscopy and the structures were reported to have singlet
D9h symmetry. Our present results show that the global minimum for FeB9
− has a
molecular wheel-like structure in triplet spin state with Cs symmetry, whereas its
heavier homologues are singlet molecular wheels with D9h symmetry. Chemical
bonding analyses show that RuB9
− and OsB9
− display a similar type of electronic
structure, where the dual σ + π aromaticity, originated from three delocalized σ bonds
and three delocalized π bonds, accounts for highly stable borometallic molecular wheels
