STRUCTURE AND STABILITY OF $CLOSO-B_{n}H_{n-1}N_{2}^{-} (n=5-12)$

Abstract

[Formula: see text], framework-isoelectronic to [Formula: see text], have been investigated at the B3LYP/6-311+G** level of theory. The most stable positional isomers of individual [Formula: see text] are similar to those of [Formula: see text] and [Formula: see text] in framework configuration. The energy analysis reveals that the cage [Formula: see text] with the icosahedron framework, [Formula: see text] with the octahedron framework and [Formula: see text] with the bicapped square antiprism framework are, in order, the most stable in the [Formula: see text] system. Furthermore, three-dimensional aromaticity of all [Formula: see text] is characterized. The most stable cages, [Formula: see text], [Formula: see text] and [Formula: see text], also have relatively large aromaticity. All the predicted N–N stretching frequencies (2127–2303 cm−1) of the most stable positional isomers in the [Formula: see text] system are lower than the computational N–N stretching frequency (2445 cm−1) of free N2 at the same level, which results from the σ donation of N2 to B frameworks. The stretching frequencies of N–N in the [Formula: see text] cages increase with the decrease of N–N distances or the increase of B–N distance. In addition, B n−1 H n−1 fragment has larger affinity for group CH than that for group BNN, namely, it favors to form the [Formula: see text] rather than the [Formula: see text].