Metallo-boranes: a class of unconventional superhalogens defying electron counting rules

Abstract

Superhalogens are a class of highly electronegative atomic clusters whose electron affinities exceed those of halogens. Due to their potential for promoting unusual reactions and role as weakly coordinating anions as well as building blocks of bulk materials, there has been considerable interest in their design and synthesis. Conventional superhalogens are composed of a metal atom surrounded by halogen atoms. Their large electron affinities are due to the fact that the added electron is distributed over all the halogen atoms, reducing electron–electron repulsion. Here, using density functional theory with a hybrid exchange–correlation functional, we show that a new class of superhalogens can be developed by doping closo-boranes (e.g., B₁₂H₁₂) with selected metal atoms such as Zn and Al as well as by replacing a B atom with Be or C. Strikingly, these clusters defy electron counting rules. For example, according to the Wade–Mingos rule, Zn(B₁₂H₁₂) and Al(BeB₁₁H₁₂) are closed-shell systems that should be chemically inert and, hence, should have very small electron affinities. Similarly, Zn(B₁₂H₁₁), Al(B₁₂H₁₂), and Zn(CB₁₁H₁₂), with one electron more than needed for electronic shell closure, should behave like superalkalis. Yet, all these clusters are superhalogens. This unexpected behavior originates from an entirely different mechanism where the added electron resides on the doped metal atom that is positively charged due to electron transfer.