Synthesis and Characterization of [Br 3 ][MF 6 ] (M=Sb, Ir), as well as Quantum Chemical Study of [Br 3 ] + : Structure, Chemical Bonding, and Relativistic Effects Compared with [XBr 2 ] + (X=Br, I, At, Ts) and [TsZ 2 ] + (Z=F, Cl, Br, I, At, Ts)

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Synthesis and Characterization of [Br 3 ][MF 6 ] (M=Sb, Ir), as well as Quantum Chemical Study of [Br 3 ] +  : Structure, Chemical Bonding, and Relativistic Effects Compared with [XBr 2 ] + (X=Br, I, At, Ts) and [TsZ 2 ] + (Z=F, Cl, Br, I, At, Ts) . / Ivlev, Sergei I.; Gaul, Konstantin; Chen, Mengyi; Karttunen, Antti J.; Berger, Robert; Kraus, Florian.

In: Chemistry - A European Journal, Vol. 25, No. 22, 17.04.2019, p. 5793-5802.

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@article{2a15377fc7d641308077bacd574c6433,
title = "Synthesis and Characterization of [Br 3 ][MF 6 ] (M=Sb, Ir), as well as Quantum Chemical Study of [Br 3 ] + : Structure, Chemical Bonding, and Relativistic Effects Compared with [XBr 2 ] + (X=Br, I, At, Ts) and [TsZ 2 ] + (Z=F, Cl, Br, I, At, Ts)",
abstract = "[Br 3 ][SbF 6 ] and [Br 3 ][IrF 6 ] were synthesized by interaction of BrF 3 with Sb 2 O 3 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) {\AA}, V=1660.01(16) {\AA} 3 , 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) {\AA}, α=85.320(8), β=82.060(7), γ=78.466(7)°, V=406.56(7) {\AA} 3 , Z=2 at 100 K. Both compounds contain the cation [Br 3 ] + , which has a bent structure and is coordinated by octahedron-like anions [MF 6 ] − (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.",
keywords = "antimony, bromine trifluoride, crystal structures, density functional calculations, tribromonium",
author = "Ivlev, {Sergei I.} and Konstantin Gaul and Mengyi Chen and Karttunen, {Antti J.} and Robert Berger and Florian Kraus",
year = "2019",
month = "4",
day = "17",
doi = "10.1002/chem.201900442",
language = "English",
volume = "25",
pages = "5793--5802",
journal = "CHEMISTRY: A EUROPEAN JOURNAL",
issn = "0947-6539",
number = "22",

}

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TY - JOUR

T1 - Synthesis and Characterization of [Br 3 ][MF 6 ] (M=Sb, Ir), as well as Quantum Chemical Study of [Br 3 ] + 

T2 - Structure, Chemical Bonding, and Relativistic Effects Compared with [XBr 2 ] + (X=Br, I, At, Ts) and [TsZ 2 ] + (Z=F, Cl, Br, I, At, Ts)

AU - Ivlev, Sergei I.

AU - Gaul, Konstantin

AU - Chen, Mengyi

AU - Karttunen, Antti J.

AU - Berger, Robert

AU - Kraus, Florian

PY - 2019/4/17

Y1 - 2019/4/17

N2 - [Br 3 ][SbF 6 ] and [Br 3 ][IrF 6 ] were synthesized by interaction of BrF 3 with Sb 2 O 3 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 (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 3 , Z=2 at 100 K. Both compounds contain the cation [Br 3 ] + , which has a bent structure and is coordinated by octahedron-like anions [MF 6 ] − (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.

AB - [Br 3 ][SbF 6 ] and [Br 3 ][IrF 6 ] were synthesized by interaction of BrF 3 with Sb 2 O 3 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 (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 3 , Z=2 at 100 K. Both compounds contain the cation [Br 3 ] + , which has a bent structure and is coordinated by octahedron-like anions [MF 6 ] − (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.

KW - antimony

KW - bromine trifluoride

KW - crystal structures

KW - density functional calculations

KW - tribromonium

UR - http://www.scopus.com/inward/record.url?scp=85063581511&partnerID=8YFLogxK

U2 - 10.1002/chem.201900442

DO - 10.1002/chem.201900442

M3 - Article

VL - 25

SP - 5793

EP - 5802

JO - CHEMISTRY: A EUROPEAN JOURNAL

JF - CHEMISTRY: A EUROPEAN JOURNAL

SN - 0947-6539

IS - 22

ER -

ID: 32969965