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Keywords:

  • boranes;
  • cluster compounds;
  • density functional calculations;
  • hyperhalogens;
  • superhalogens

Abstract

Super- and hyperhalogens are a class of highly electronegative species whose electron affinities far exceed those of halogen atoms and are important to the chemical industry as oxidizing agents, biocatalysts, and building blocks of salts. Using the well-known Wade–Mingos rule for describing the stability of closo-boranes BnHn2− and state-of-the-art theoretical methods, we show that a new class of super- and hyperhalogens, guided by this rule, can be formed by tailoring the size and composition of borane derivatives. Unlike conventional superhalogens, in which a central metal atom is surrounded by halogen atoms, the superhalogens formed according to the Wade–Mingos rule do not have to have either halogen or metal atoms. We demonstrate this by using B12H13 and its isoelectronic cluster CB11H12 as examples. We also show that while conventional superhalogens containing alkali atoms require at least two halogen atoms, a single borane-like moiety is sufficient to give M(B12H12) clusters (M=Li, Na, K, Rb, Cs) superhalogen properties. In addition, hyperhalogens can be formed by using the above superhalogens as building blocks. Examples include M(B12H13)2 and M(CB11H12)2 (M=Li–Cs). This finding opens the door to an untapped source of superhalogens and weakly coordinating anions with potential applications.