Ionic-liquid-assisted synthesis of the phosphorus interhalides [PBr4][IBr2] and [PBr4][I5Br7]. Issue 41 (28th September 2016)

• Record Type: Journal Article
• Authors: Hausmann, David; Köppe, Ralf; Wolf, Silke; Roesky, Peter W.; Feldmann, Claus
• Is Part Of: Dalton transactions. Volume 45:Issue 41(2016)
• Page Start: 16526
• Page End: 16532
• Publication Date: 2016-09-28
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c6dt03303b
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Ionic-liquid based synthesis results in the phosphorus interhalides [PBr4 ][IBr2 ] and [PBr4 ]2 [I5 Br7 ] whereof the latter shows thermal halogen release of 96.8 wt% (≤300 °C). Abstract : The phosphorus interhalides [PBr4 ][IBr2 ] (1 ) and [PBr4 ]2 [I5 Br7 ] (2 ) were prepared by reaction of PBr5 and the interhalogen IBr in the ionic liquid [MeBu3 N][N(Tf)2 ] (N(Tf)2 : bis(trifluoromethylsulfonyl)amide). [PBr4 ][IBr2 ] (1 ) consists of tetrahedral [PBr4 ] + cations and linear [IBr2 ] − anions. [PBr4 ]2 [I5 Br7 ] (2 ) also contains [PBr4 ] + cations as well as the iodine bromide anion [I5 Br7 ] 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.