Nitrogen versus carbon in planar pentacoordinate environments supported by Be 5 H n rings.

NBe 5 H n n -3 ( n = 0-5) (0A-5A) species with a novel planar pentacoordinate nitrogen (ppN) were designed by the isoelectronic substitution of the C atom in planar pentacoordinate carbon (ppC) species CBe 5 H n n -4 ( n = 0-5) with an N atom. The highly flexible H atoms found in ppC species CBe 5 H 2 2- and CBe 5 H 3 - were fixed upon the nitrogen substitution, as mirrored by the non-flexible H atoms in their ppN analogues NBe 5 H 2 - (2A) and NBe 5 H 3 (3A). Moreover, the N atom was found to fit the H-surrounded Be 5 rings better than the C atom because the ppC species CBe 5 H 4 and CBe 5 H 5 + adopted non-planar structures due to size-mismatch between the C atom and the H-surrounded Be 5 ring, but their ppN analogues NBe 5 H 4 + (4A) and NBe 5 H 5 2+ (5A) adopted perfect planar structures. The electronic structure analyses revealed that the N atoms in 0A-5A were involved in four doubly occupied orbitals, including three six-center two-electron (6c-2e) σ bonds and one 6c-2e π bond. Therefore, these ppN species not only obey the octet rule, but also possess the interesting σ and π double aromaticity, which contributes to the stabilization. Consequently, 2A, 4A, and 5A are charged kinetically viable global energy minima, and are suitable for the gas phase generation and spectroscopic characterization.