Double aromaticity in transition metal centered double-ring boron clusters M@B2n (M = Ti, Cr, Fe, Ni, Zn; n = 6, 7,...

It is well known that double-ring boron clusters have got the special double aromaticity with delocalized π orbitals in two directions (tangential and radial), which are potential ligands centered by a transition metal. In this article, the transition metal centered double-ring boron clusters M@B2n (M = Ti, Cr, Fe, Ni, Zn; n = 6, 7, 8) are theoretically investigated by density functional theory calculations. These endohedral compounds have also got double aromaticity in both tangential and radial directions. Interestingly, the tangential delocalized π orbitals of boron ligands following the Huckle's (4n + 2) rule do not interact with the central metal, while the radial π orbitals of boron ligands are bonded with the central mental to form spd-π endohedral bonding. The spd-π endohedral bonding follows the 18e-principle in Ni@B14 and Fe@B16. However, due to the flat shape of the compounds, 14e (Cr@B14) and 16e (Ni@B12) can also be electronically very stable where the energy levels of the spd-π orbitals delocalized in z-direction rise up. This intriguing bonding model makes sense in further study of the boron chemistry.