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
AN - SCOPUS:85063581511
SN - 0947-6539
VL - 25
SP - 5793
EP - 5802
JO - Chemistry: A European Journal
JF - Chemistry: A European Journal
IS - 22
ER -