Br4F21]- - a unique molecular tetrahedral interhalogen ion containing a μ4-bridging fluorine atom surrounded by BrF5 molecules.

Abstract

The reaction of [NMe4][BrF6] with an excess of BrF5 leads to the compound [NMe4][Br4F21]·BrF5. It features molecular [(μ4-F)(BrF5)4]- anions of tetrahedron-like shape containing central μ4-bridging F atoms coordinated by four BrF5 molecules. It is the most BrF5-rich fluoridobromate anion by mass. Quantum-chemical calculations showed that the μ4-F-Br bonds within the anion are essentially ionic in nature. The compound is the first example where F atoms bridge μ4-like neither to metal nor to hydrogen atoms. It was characterized by Raman spectroscopy and by single-crystal X-ray diffraction. The latter showed surprisingly that its crystal structure is related to the intermetallic half-Heusler compound and structure type MgAgAs.