Abstract
In this chapter we have shown that boron has two faces in chemistry: with classical and multicenter bonding. When neutral boron atoms are involved in bonding, we usually encounter domination of multicenter bonding. Such examples are planar, quasi-planar, and three dimensional pure and doped boron clusters, two-dimensional sheets as well as conventional deltahedral boranes. However, when a boron atom acquires an extra electron, it tends to form molecules similar to those of the neighboring carbon featuring classical 2c-2e σ-bonds instead of multicenter ones. Such examples are BH4 −, analog of the CH4 molecule; LinBnH2n+2 molecules containing BnH2n+2 n− kernels, which are isostructural to corresponding molecules in the CnH2n+2 series; Li6B6H6, analog of benzene; linear chain of boron anions in LiBx, analog of carbine; and 2D layer of boron in MgB2 mimicking the graphene structure. Chemistry of boron continues to expand conquering new territories and providing us with unprecedented structures, chemical bonding, internal rotations and other unusual properties. We believe we are at the beginning of new era of boron chemistry.
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Popov, I.A., Boldyrev, A.I. (2015). Classical and Multicenter Bonding in Boron: Two Faces of Boron. In: Hnyk, D., McKee, M. (eds) Boron. Challenges and Advances in Computational Chemistry and Physics, vol 20. Springer, Cham. https://doi.org/10.1007/978-3-319-22282-0_1
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