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

Abstract

The phosphorus interhalides [PBr][IBr] (1) and [PBr][IBr] (2) were prepared by reaction of PBr and the interhalogen IBr in the ionic liquid [MeBuN][N(Tf)] (N(Tf): bis(trifluoromethylsulfonyl)amide). [PBr][IBr] (1) consists of tetrahedral [PBr] cations and linear [IBr] anions. [PBr][IBr] (2) also contains [PBr] cations as well as the iodine bromide anion [IBr]. The latter represents the yet largest known polyiodinebromide. Moreover, (2) shows remarkable halogen release (IBr and Br) 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.

Ionic‐Liquid‐Based Synthesis of the Bromine‐Rich Bromidoplatinates [NBu3Me]2[Pt2Br10](Br2)2 and [NBu3Me]2[Pt2Br10](Br2)3

“…It needs to be noted that 2 is only formed in the presence of SiBr 4 . We have frequently observed such effect related to the presence of strong Lewis acids such as SiBr 4 , SnBr 4 , or SnI 4 , . Although the respective species remain in solution subsequent to the reaction, the abstraction of Br – by SiBr 4 and the resulting influence on the total stoichiometry – especially on the Br – ‐to‐Br 0 ratio of the reaction – can be rationalized as highly relevant.…”

Polyhalogen and Polyinterhalogen Anions from Fluorine to Iodine

“…[145] Thel argest known dianions of polyiodinechloride and -bromide are [PPh 4 ] 2 [I 6 Cl 6 ]( disordered:[ PPh 4 ] 2 [I 4 Cl 8 ]) [147] and [PBr 4 ] 2 [I 5 Br 7 ]; Figure 41). [188] [PPh 4 ] 2 [I 6 Cl 6 ]w as obtained in the reaction of [PPh 4 ]Cl with three equivalents of ICl. TheV -shaped [I 2 Cl 3 ] À anions are bridged over the central chlorine atoms via an iodine molecule that is disordered with 28.5 %c hlorine.…”

[NMe4][I4Br5]: A new Iodobromide from an Ionic Liquid with Halogen–Halogen Interactions

“…Note: During the publication process another article related to our investigation was published by the Feldmann group . They described two phosphorus interhalides [PBr 4 ][IBr 2 ], with almost linear [IBr 2 ] − anions, and the yet largest known polyiodinebromide dianion [PBr 4 ][I 5 Br 7 ] which were synthesized in an ionic‐liquid.…”