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Triarylphosphanes react with elemental bromine to give triarylbromophosphonium bromides. With an excess of bromine larger polybromides are formed. The influence of the stepwise fluorination of the cation on the formed polybromide anion was investigated. The polybromide dianions and networks [(C6H5)3PBr]2[Br14], [(C6H4F)3PBr]2[Br14], [(C6H4F)3PBr][Br11], [(C6H2F3)3PBr]2[Br16], and [(C6F5)3PBr]2[Br20]·Br2 were obtained and characterized by Raman spectroscopy, single‐crystal X‐ray structure determination and quantum‐chemical calculations at the RI‐B3LYP‐D3/def2‐TZVPP level. Additionally, two further [Br20]2– dianions, [BMDIM][Br20] {BMDIM = 1,12‐bis[(1‐methylbenzimidazolium)‐3‐yl]dodecane} and [AsPh4]2[Br20]·0.5Br2, are presented and compared to all known eicosabromide dianions.
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Mann et al. (2018) studied this question.
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