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Chen, Mengyi
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article
Synthesis and Characterization of [Br 3 ][MF 6 ] (M=Sb, Ir), as well as Quantum Chemical Study of [Br 3 ] +
Abstract
<p>[Br<sub>3</sub>][SbF<sub>6</sub>] and [Br<sub>3</sub>][IrF<sub>6</sub>] were synthesized by interaction of BrF<sub>3</sub>with Sb<sub>2</sub>O<sub>3</sub>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<sup>3</sup>, Z=8 at 100 K. The latter compound crystallizes in the triclinic space group P (Formula presented.) (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<sup>3</sup>, Z=2 at 100 K. Both compounds contain the cation [Br<sub>3</sub>]<sup>+</sup>, which has a bent structure and is coordinated by octahedron-like anions [MF<sub>6</sub>]<sup>−</sup>(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.</p>