Synthesis and Characterization of [Br3][MF6] (M=Sb, Ir), as well as Quantum Chemical Study of [Br3]+ Structure, Chemical Bonding, and Relativistic Effects Compared with [XBr2]+ (X=Br, I, At, Ts) and [TsZ2]+ (Z=F, Cl, Br, I, At, Ts). Issue 22 (25th March 2019)

• Record Type: Journal Article
• Authors: Ivlev, Sergei I.; Gaul, Konstantin; Chen, Mengyi; Karttunen, Antti J.; Berger, Robert; Kraus, Florian
• Is Part Of: Chemistry. Volume 25:Issue 22(2019)
• Page Start: 5793
• Page End: 5802
• Publication Date: 2019-03-25
• Subjects: antimony -- bromine trifluoride -- crystal structures -- density functional calculations -- tribromonium; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201900442
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: [Br3 ][SbF6 ] and [Br3 ][IrF6 ] were synthesized by interaction of BrF3 with Sb2 O3 or iridium metal, respectively. The former compound crystallizes in the orthorhombic space group Pbcn (No. 60) with a =11.9269(7), b =11.5370(7), c =12.0640(6) Å, V =1660.01(16) Å 3, Z =8 at 100 K. The latter compound crystallizes in the triclinic space group P 1 ‾ (No. 2) with a =5.4686(5), b =7.6861(8), c =9.9830(9) Å, α =85.320(8), β =82.060(7), γ =78.466(7)°, V =406.56(7) Å 3, Z =2 at 100 K. Both compounds contain the cation [Br3 ] +, which has a bent structure and is coordinated by octahedron‐like anions [MF6 ] − (M=Sb, Ir). Experimentally obtained cell parameters, bond lengths, and angles are confirmed by solid‐state DFT calculations, which differ from the experimental values by less than 2 %. Relativistic effects on the structure of the tribromonium(1+) cation are studied computationally and found to be small. For the heaviest analogues containing At and Ts, however, pronounced relativistic effects are found, which lead to a linear structure of the polyhalogen cation. Abstract : Tribromonium compounds : The crystal structures of the two tribromonium compounds, [Br3 ][SbF6 ] and [Br3 ][IrF6 ], are reported and trends in electronic structure of the tribromonium cation and derivatives thereof are analyzed (see figure).