Borane Derivatives: A New Class as Super and Hyperhalogens

TL;DR

This paper introduces a novel class of super and hyperhalogens based on borane derivatives, expanding the understanding of highly electronegative species beyond traditional halogen and metal-based structures using Wade-Mingos rule and theoretical methods.

Contribution

It demonstrates that borane derivatives can form super and hyperhalogens without halogen or metal atoms, revealing new possibilities for designing highly electronegative compounds.

Findings

Borane derivatives can be tailored to form superhalogens without halogen or metal atoms.

Single borane-like moieties are sufficient to produce superhalogen properties in clusters.

Hyperhalogens can be constructed by using superhalogens as building blocks.

Abstract

Super and hyperhalogens are a class of highly electronegative species whose electron affinities far exceed those of halogen atoms and are important to chemical industry as oxidizing agents, bio-catalysts, and building blocks of salts. Using Wade-Mingos rule well known for describing the stability of closo-boranes (BnHn2-) and state of the art theoretical method 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 which have a metal atom at the core surrounded by halogen atoms, the superhalogens formed using 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, only one borane-like moiety is sufficient to render M(B12H12) (M=Li, Na, K, Rb, Cs) clusters superhalogen properties. In addition, hyperhalogens can be formed by using the above superhalogens as building blocks. Examples include M(B12H13)2 and M(C-B11H12)2 (M=Li - Cs). This finding opens the door to an untapped source of superhalogens and weakly coordinating anions with potential applications.