Fluxional Boron Clusters: From Theory to Reality

ConspectusIsolated boron clusters exhibit many intriguing properties, which have only recently been unfolding with the hand-in-hand advancement of state-of-the-art experimental and theoretical methods for the analyses of their electronic structure, chemical reactivity, and nuclear dynamics. A fascinating property that a number of these clusters display is fluxionality, a dynamical phenomenon associated with the delocalized nature of the chemical bonding and related to the continuous exchange between interatomic neighbors. The electron-deficient nature of boron is the driving force behind its extraordinary ability to form multicenter bonds, and this in turn leads to fluxional behavior only when an appropriate combination of topology and bonding is present. The first instance of fluxionality in boron clusters, the quasi-planar anion B19−, was reported in 2010. The rotational barrier of the inner B6 unit spinning within the peripheral B13 ring can be overcome even at low temperature, mimicking the characteri...