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)

Abstract

[Br3][SbF6] and [Br3][IrF6] were synthesized by interaction of BrF3 with Sb2O3 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) Å3, Z=8 at 100 K. The latter compound crystallizes in the triclinic space group Ptrue1‾ (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) Å3, 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.

Polyhalogen and Polyinterhalogen Anions from Fluorine to Iodine

“…In contrast to the presently underexplored polyhalogen cations, of which only a few examples exist, the diversity of polyhalogen anions is significantly greater. In addition, significant efforts are currently being devoted to the exploration of unusual polyhalogen cations, such as triinterhalogen cations containing the heavy halogens bromine, astatine, and tennessine …”

Pressure-induced second-order phase transition in fluorine

“…In flat regions with small curvature, the step size tends to be large, and the algorithm may miss a minimum due to an oversized step. The optimization convergence tests were performed using the experimentally determined structure for α-F 2 10 relaxed using the default CRYSTAL17 optimization parameters as the starting point.…”

“…Despite the much higher computational cost, we chose the hybrid functional PBE0 (including a contribution from an exact Hartree–Fock exchange term) to investigate the C 2/ c → Cmce phase transition in fluorine, as it has been successfully used in the computer investigation of fluorine before. 10 In this functional, 25% of the exchange energy is calculated exactly using Hartree–Fock theory. Furthermore, a computationally efficient way to account for the missing long-range correlation interactions in standard DFT is to add, a posteriori , an dispersive energy term that is dependent solely on the interatomic distances.…”

Polyhalogen‐ und Polyinterhalogen‐Anionen von Fluor bis Iod

“…Dabei soll nicht unerwähnt bleiben, dass beträchtliche Anstrengungen unternommen werden, um auch ungewöhnliche Polyhalogen‐Kationen herzustellen, z. B. Untersuchungen von Triinterhalogen‐Kationen der schwereren Halogene Brom, Astat und Tenness …”

“…B. Untersuchungen von Tr iinterhalogen-Kationen der schwereren Halogene Brom, Astat und Te nness. [15] Die hier beschriebenen, negativ geladenen Polyhalogene werden in der Folge als Polyhalogen-Anionen bezeichnet. Die Bezeichnung "Polyhalogenide" wird hier der Kürze wegen ebenfalls verwendet, wenn der Kontext eindeutig ist.…”