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

Abstract

The bromine‐rich bromidoplatinates(IV) [NBu3Me]2[Pt2Br10](Br2)2 (1) and [NBu3Me]2[Pt2Br10](Br2)3 (2) were prepared by reaction of PtBr4 and elemental bromine in the ionic liquid [MeBu3N][N(Tf)2] [N(Tf)2 = bis(trifluoromethylsulfonyl)amide]. Both bromine‐rich bromidoplatinates(IV) contain [Pt2Br10]2– anions and [NBu3Me]+ cations as voluminous building units with an almost identical structural arrangement and very similar unit cells. The difference of the title compounds is related to the specific number of Br2 molecules that link the [Pt2Br10]2– anions to three‐dimensional networks. Whereas 1 is relatively stable under inert conditions, 2 releases bromine even at ambient pressure. The title compounds are characterized by single‐crystal structure analysis and Raman spectroscopy.

1D and 2D Polybromotellurates(IV): Structural Studies and Thermal Stability

“…Raman spectroscopy is widely used in characterization of polyhalides, including polybromides . Raman spectra of 1 – 3 are similar (Figure ), featuring strong peaks at 272, 265 and 271 cm –1 , respectively, are assigned to {Br 2 } units, and comparable with those observed in related polybromides of Cu (260 and 257) and Pt (262 and 277 cm –1 , respectively).…”

Opening the Third Century of Polyhalide Chemistry: Thermally Stable Complex with “Trapped” Dichlorine

“…In somec ases, this methodp ermits "capture" of unusual polyhalide speciess uch as T-shaped planar {Br 9 } 4À . [21] Such hybrid polyhalogen-connected halometalates often possessr emarkable thermal stability.S imilar observations were made by Feldmann for Cu, Zn and Pt halides; [22][23][24] moreover,d etailed analysis of available structural data reveals [25] that examples of such polyhalogen-halometalate hybridsw ere known earlier, [26][27][28][29] but often remained overlooked. Based on our experience and analysis of availabled ata, we decided to try "trapping" of dichlorine or polychlorides in supramolecular assemblies with chloro complexes.…”

The Bromine‐Rich Bromido Metallates [BMIm]2[SnBr6]·(Br2) and [MnBr(18‐crown‐6)]4[SnBr6]2·(Br2)4.5

“…For the strong Br–Br bond, a value of f (Br–Br): 1.78 × 10 2 and a value f (Br ··· Br): 0.28 × 10 2 N m –1 for the weak bond can be obtained. Taking the simplicity of this procedure into account, we assume the bonding in 2 to be comparable to that in the bromine‐rich bromido platinate [NBu 3 Me] 2 [Pt 2 Br 10 ] · (Br 2 ) 2 , having a weak Br ··· Br bond of f (Br ··· Br): 0.36 × 10 2 and a strong Br–Br bond of f (Br–Br): 1.57 × 10 2 N m –1 . To classify the strength of the Br–Br bonds in terms of formal bond orders like 1.5, 1.0 and 0.5, the force constants and bond energies D 0 0 of the series Br 2 + , Br 2 , Br 2 – are given for comparison (Br 2 + : 3.34 × 10 2 N m –1 , 315 kJ mol –1 ; Br 2 : 228 pm, 2.46 × 10 2 N m –1 , 237 kJ mol –1 ; Br 2 – : 0.58 × 10 2 N m –1 , 111 kJ mol –1 ) , …”

“…Typical examples of bromine‐containing metal bromides are [Me 4 N] 3 [Sb 2 Br 9 ](Br 2 ), [(Me 3 P)AuBr 3 ](Br 2 ), [Bu 4 N][PtBr 4 Cl 2 ](Br 2 ) 6 , or [Bu 4 N] 2 [Pt 2 Br 10 ](Br 2 ) 7 . Based on our studies in ionic liquids, we could also add the compounds [P( o ‐tolyl) 3 Br] 2 [Cu 2 Br 6 ](Br 2 ), [NBu 3 Me] 2 [Pt 2 Br 10 ](Br 2 ) 2 and [NBu 3 Me] 2 [Pt 2 Br 10 ](Br 2 ) 3 …”