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Bromine Pentafluoride BrF5, the Formation of [BrF6]− Salts, and the Sterical (In)Activity of the Br Lone Pairs

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BrF 5 can be prepared by the reaction of BrF 3 with fluorine under UV light in the region of 300 to 400 nm at room temperature. It was analyzed by UV-Vis, NMR, IR and Raman spectroscopy. Its crystal structure was redetermined by X-ray diffraction and the space group corrected to Pnma . Quantum chemical calculations were performed for the band assignment of the vibrational spectra. A monoclinic polymorph of BrF 5 was quantum chemically predicted and then observed as its low-temperature modification in space group P 2 1 / c by single crystal diffraction. BrF 5 reacts with the alkali metal fluorides A F ( A = K, Rb) to form alkali metal hexafluoridobromates(V), A [BrF 6 ] whose crystal structures have been determined. Both compounds crystallize in the K[AsF 6 ] structure type ( R [[EQUATION]] , no. 148, hR 24). For the species [BrF 6 ] + , BrF 5 , [BrF 6 ] − and [IF 6 ] − the chemical bonds and lone pairs on the heavy atoms were investigated by means of Intrinsic Bond Orbital analysis.

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