Issue 41, 2016

Ionic-liquid-assisted synthesis of the phosphorus interhalides [PBr4][IBr2] and [PBr4][I5Br7]

Abstract

The phosphorus interhalides [PBr4][IBr2] (1) and [PBr4]2[I5Br7] (2) were prepared by reaction of PBr5 and the interhalogen IBr in the ionic liquid [MeBu3N][N(Tf)2] (N(Tf)2: bis(trifluoromethylsulfonyl)amide). [PBr4][IBr2] (1) consists of tetrahedral [PBr4]+ cations and linear [IBr2] anions. [PBr4]2[I5Br7] (2) also contains [PBr4]+ cations as well as the iodine bromide anion [I5Br7]2−. The latter represents the yet largest known polyiodinebromide. Moreover, (2) shows remarkable halogen release (IBr and Br2) of 96.8 wt% below 300 °C. For the ternary system P–Br–I, (1) and (2) are the first compounds that were characterized by crystal structure analysis. Composition, bonding situation and properties were further validated by energy dispersive X-ray (EDX) analysis, thermogravimetry (TG) and Raman spectroscopy.

Graphical abstract: Ionic-liquid-assisted synthesis of the phosphorus interhalides [PBr4][IBr2] and [PBr4][I5Br7]

Associated articles

Supplementary files

Article information

Article type
Paper
Submitted
22 Aug 2016
Accepted
22 Sep 2016
First published
23 Sep 2016

Dalton Trans., 2016,45, 16526-16532

Ionic-liquid-assisted synthesis of the phosphorus interhalides [PBr4][IBr2] and [PBr4][I5Br7]

D. Hausmann, R. Köppe, S. Wolf, P. W. Roesky and C. Feldmann, Dalton Trans., 2016, 45, 16526 DOI: 10.1039/C6DT03303B

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