Bromine Monofluoride

Article abstract of DOI:10.1002/zaac.201200293

BrF can be prepared by reaction of Br₂ and F₂ in various solvents below -100 °C. In solution it is identified by ¹⁹F NMR and Raman spectroscopy. From CH₃Cl solution a single crystal structure determination of a BrF/CH₃Cl adduct was obtained. The preparationfrom BrF3 and Br₂ at 600 °C also delivers BrF in small amounts. The crystal structure of BrCl comes in an ordered and a disordered variety. The ordered structure is made of Br- Cl···Br-Cl chains. Computations suggest that neat BrF crystallizes in a dipol-dipole type polymeric structure rather than a halogen bonded one as in ClF. A possible intermediate along the decomposition pathway into BrF3 and Br₂ is Br- BrF2.

Full text of DOI:10.1002/zaac.201200293

Job/Unit: Z12293
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Date: 07-08-12 17:07:24
Pages: 6
ARTICLE
DOI: 10.1002/zaac.201200293
Bromine Monofluoride
Thomas Drews[a] and Konrad Seppelt*[a]
Dedicated to Professor Rudolf Hoppe on the Occasion of His 90th Birthday
Keywords: Bromine monofluoride; NMR spectroscopy; Raman spectroscopy; Bromine; Fluorine; Crystal structure
Abstract. BrF can be prepared by reaction of Br2 and F2 in various The ordered structure is made of Br–Cl···Br–Cl chains. Computations
solvents below –100 °C. In solution it is identified by 19F NMR and suggest that neat BrF crystallizes in a dipol-dipole type polymeric
Raman spectroscopy. From CH3Cl solution a single crystal structure structure rather than a halogen bonded one as in ClF. A possible inter-
determination of a BrF/CH3Cl adduct was obtained. The preparation mediate along the decomposition pathway into BrF3 and Br2 is Br–
from BrF3 and Br2 at 600 °C also delivers BrF in small amounts. The BrF2.
crystal structure of BrCl comes in an ordered and a disordered variety.
Introduction
Results and Discussion
We obtained BrF in two ways, first by com-proportionation
of BrF3 and Br2 at 600 °C, as suggested previously.[14] This
mixture is heated in a monel autoclave and released into a
vacuum at –196 °C. The yellow product is dissolved in C2H5F
at –100 °C. The NMR spectrum showed the presence of BrF,
but the major products are still Br2 and BrF3, as shown by
Raman spectroscopy.
Alternatively Br2 was treated in solution with elemental flu-
orine (20% in nitrogen) between –95 °C and –110 °C in vari-
ous solvents (see Table 1). The same method was tried before
at –78 °C in CFCl3, but the only product obtained was very
pure BrF3.[15] The choice of solvents is limited. CFCl3 and
other chlorofluorocarbons do not dissolve Br2 enough at
–100 °C. Propionitrile works well but BrF reacts with it slowly
even at this temperature. The solvents CH3Cl, C2H5F, and
CH3F worked best, but due to their low boiling point the pro-
cedure is tricky. CH2Cl2 works also fine, however Br2 is not
soluble enough in CH2F2. So we thought that CH2ClF might
be a good compromise. Strangely enough CH2ClF reacts ex-
Simple, binary compounds have a principle importance, e.g.
for the test of theoretical models. A historic and famous exam-
ple is the detection of noble gas fluorides in 1962,[1,2,3] that
came at a time when theoretical modelation has already been
possible. The related halogen fluorides are known much
longer, however. It is the merit of Otto Ruff to have prepared
many of them for the first time.[4] The only latecomers here
[5]
are ClF5 and IF3.[6] The diatomic inter halogen compounds
X–Y have been the starting point of the electronegativity scale
by L. Pauling.[7] The prediction there has been that their sta-
bility against decomposition into the elements would be largest
if the electronegativity differences between X and Y are largest.
IF and BrF should be particularly stable. This is certainly true,
but both disproportionate rapidly into IF5 and I2 and BrF3 and
Br2.
Of course the molecule BrF exists in the gas phase, it was
detected by spectroscopic methods[8,9] or in matrices.[10] Also
it is an obvious intermediate in addition reactions:
SF4 + BrF3 / Br2 / CsF Ǟ SF5Br[11]
[12]
CF3–CF=CF2 + BrF3/Br2 Ǟ CF3–CBrF–CF3
In the following we show that BrF can indeed be obtained Table 1. 19F NMR chemical shifts and Raman lines of BrF in various
solvents.
in substance, but it is very unstable. Without diminishing the
19F NMR /ppm
Raman /cm–1
543
merits of O. Ruff it must be stated that his description of BrF
as an orange compound, melting around –35 °C and boiling
under decomposition around 20 °C, cannot be correct.[13] If
BrF would be similarly weakly associated in the condensed
phases as ClF we extrapolated a boiling point of about –65 °C!
C2H5CN
CH3CN/CH2Cl2
CH3Cl
–288.2
–285.7
–349.9
–371.6
–388.2
–452.0
–453.9
585
569
CH2Cl2
CH2ClFa)
C2H5F
633
637
661
CH3F
* Prof. Dr. K. Seppelt
Matrixb)
Gas IRc)
E-Mail: Seppelt@chemie.fu-berlin.de
[a] Institut für Chemie, Anorganische und Analytische Chemie
Freie Universität Berlin
662.3 / 660.7 79/81BrF
a) This value is obtained from a reaction in CH3F and subsequent
addition of CH2ClF. b) Ref. [10]. c) Reference[9]
Fabeckstr. 34–36
14195 Berlin, Germany
.
Z. Anorg. Allg. Chem. 0000, ᭿,(᭿), 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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T. Drews, K. Seppelt
ARTICLE
plosively with 20% F2 in nitrogen even at –100 °C, while in
CH2Cl2 and CH2F2 only traces of fluorination products are
detected at –100 °C.[16]
Usually the reaction is done in 5 mm NMR tubes so that 19
F
NMR spectra can be taken directly. In those cases, in which
Br2 does not dissolve completely at –100 °C it is dissolved at
higher temperatures and the solution is shock frozen to
–196 °C to obtain very finely divided Br2. During the fluorina-
tion the yellow-orange color of the solution lightens up, and
un-dissolved Br2 goes into solution. In Table 1 the NMR and
Raman data are collected.
The 19F NMR spectra show clearly the advent of a new
compound with an extreme high field shift, besides traces of
solvent fluorination products that usually can be identified, see
Figure 1. Since ClF (–419.4 ppm[17]) and related low valent
main group fluorides like CF3–S–F (–351 ppm[18]) or R–Se–F
(–312.8 to –371.0 ppm[19]) have similar high field shift reso-
nances, we were certain that BrF has been formed. BrF3 ap-
pears only after excess fluorination or after warming with a
broad signal around –22 ppm. Another characteristic of the
BrF NMR signal is the extreme solvent shift. It is obvious that
increasing donor strengths of the solvents shifts the resonance
dramatically to lower field (Table 1). It is safe to assume that
pure BrF would have shifts close to those observed in CH3F
and C2H5F solutions since these solvents can be considered as
extremely low basic.
Figure 2. Raman spectrum of BrF in CH3Cl at –100 °C. Raman lines
of CH3Cl with higher wave numbers are cut off.
tial linear array Cl···Br–F (179.0°) is a clear indication. The
interaction between the two adduct components is considered
to be weak: The Br–F bond length [182.2(2) pm] is only a
little longer than the bond length in the gaseous state, which
was obtained from the microwave spectrum of 79Br–F
[175.9(10) pm[20]] The C–Cl bond length in the adduct has
increased to 179.8(3) pm as compared to gaseous CH3Cl
[177.60(3) pm)[21]], whereas the Br···Cl distance is
264.0(2) pm. The bond length of the single bond in BrCl is
217.9(2) pm, see below.
Figure 3. Structure of BrF·CH3Cl in the crystal, Ortep representation,
50% displacement ellipsoids.
We were not able to crystallize BrF without solvent. For this
case the extreme low basic solvents C2H5F and CH3F were
tested. Indeed, BrF precipitates below –130 °C as a fine, yel-
low powder that can be re-dissolved at –100 °C. Evaporation
of the solvent to dryness at –130 °C induced decomposition
into BrF3 and Br2. It seems that BrF is only stable in the pres-
ence of a donor solvent, even if these are such a weak donors
like CH3F and C2H5F.
So the crystal structure of neat BrF remains unknown. This
would be of interest in the light of the crystal structures of ClF
and BrCl. In ClF the dominating intermolecular interactions
are between the chlorine atoms resulting in a zig-zag chain
with “terminal” fluorine atoms.[22] This is a very simple exam-
ple of so called halogen bonding.
Figure 1. 19F NMR spectrum of BrF in CH3Cl at –100 °C. The tiny
signals between –20 and –260 ppm are BrF3 and fluorination products
of CH3Cl: –28.3 ppm, broad, BrF3; –73.0 ppm doublet, JHF = 63.6 Hz,
CHF3; –143.1 ppm, triplet, JHF = 98.3 Hz, CH2F2; –170.0 ppm, triplet,
JHF = 96.8 Hz, CH2ClF; –267.3 ppm, quartet, JHF = 138.7 Hz, CH3F.
The Raman spectra in solution show the BrF vibration be-
tween 543 and 637 cm–1. These values also have a strong sol-
vent shift that parallels the 19F NMR shifts: Higher basicity of
the solvent decreases the Br–F frequency. This is also interpre-
ted as a donor acceptor complex formation solvent Br–F in
solution (Figure 2).
The crystal structure of BrCl is to the best of our knowledge
unknown. Crystals of yellow BrCl are easily obtained at
Crystal Structure of BrF···CH3Cl
Once formed BrF is very soluble in the named solvents. –78 °C, they come in two modifications. The first modification
Only in case of CH3Cl we were able to crystallize it (see Fig- is nothing but a rotational disordered Cl2 or Br2 type structure,
ure 3). It appears as adduct with CH3Cl. Obviously the chlo- where bromine and chlorine are not discriminated. Lattice con-
rine atom acts as donor to the bromine atom in BrF. The essen- stants, positional parameters, and bond length are very close
2
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Bromine Monofluoride
Table 2. X-ray results of the disordered BrCl modifications, all spaces groups are Cmca.
a /pm
b /pm
c /pm
V /106pm3
T /°C
a)
Br2
665.67(4)
622.35(2)
645.1(2)
455.4(3)
445.61(1)
447.1(2)
870.68(5)
817.85(2)
846.5(2)
263.95
226.8
244.15
–103 °C
–173 °C
–160 °C
Br–Br = 230.1(2) pm
Cl–Cl = 199.4(2) pm
Br–Cl = 220.5(1) pm
a)
Cl2
BrCl
a) B. M. Powell, K. M. Heal, B. H. Torrie, Mol. Phys. 1984, 53, 929–939.
to the averaged numbers of the known Br2 and Cl2 structures
within the same space group Cmca (see Table 2).
In the ordered structure the bromine and chlorine positions
are separated, although the lattice parameters have hardly
changed. The Br–Cl bond length is 217.8(2) pm. This com-
pares to 214 pm in the free molecule.[23]
In the crystal the Br–Cl molecules are arranged in a zig-zag
chain with close Br···Cl contacts is found (see Figure 4), quite
similar to the long known structure of ICl.[24]
In the Br–F system BrF3/Br2 is the most stable composition,
when the strong interaction of BrF3 molecules is taken into
account, which is also experimentally established. Dimeriza-
tion of BrF molecules results in a slight preference for the
FBr···FBr combination over the FBr···BrF configuration by
0.38 kcal·mol–1. In order to arrive at a more realistic model for
the condensed phase we calculated a tetramer (FBr···BrF)2 and
a hexamer (FBr···FBr)3. These cyclic oligomers were chosen
since they have realistic bridge angles which are also expected
in polymer chain arrangements. Herein also a preference of the
FBr···FBr interaction is observed over the FBr···BrF interaction
(0.6 kcal·mol–1) (however (FI···IF)2 seems to be more stable
than (FI···FI)3!).
The dimerization of BrF into Br–BrF2, FBr···BrF, and
FBr···FBr has already been calculated before by various DFT
methods.[25] The relative energies vary somewhat, but overall
similar qualitative similar results are obtained.
Our calculations also show that the stabilization of BrF by
CH3F and more so by CH3Cl can prevent the disproportiona-
tion into BrF3 + Br2. Some of the calculated structures of the
BrF system are shown in Figure 6.
One interesting local minimum is the T-shaped compound
Br–BrF2. This has been possibly found in a matrix isolation
study[10] but identified only by one absorption in the IR (at
555 cm–1, νasBrF2). We have calculated the whole vibrational
spectrum, and the most characteristic line should be the Br–Br
stretching mode at around 300 cm–1 (see Table 3). But this is
very close to the Br–Br stretching mode in Br2 (316 cm–1 dis-
solved, 296 cm–1 solid), which is extremely intense in the Ra-
man spectrum, so that any Br–BrF2 might be obscured in our
Figure 4. The ordered crystal structure of Br–Cl, showing a similar
chain as in ICl. Ortep representation, 50% probability, displacement
ellipsoids.
For BrF the question is whether the larger atom size in BrF
versus ClF would favor a halogen bond structure as in ClF, or
whether the larger dipole momentum in BrF versus ClF would
favor a BrCl or ICl like structure. Experimentally we cannot
answer this question.
In order to arrive at least at a guess we have computed the
BrF system (see Figure 5), also some calculations of the ClF
and IF system are included.
These MP2 calculations reproduce some long known experi-
mental facts: ClF and ClF3/Cl2 are close to equilibrium, while
the IF5/I2 combination is by far the most stable composition
for “IF”.
Figure 5. Energetics of the BrF system, as compared to the ClF and IF system. Molecular ClF, BrF, and IF are set arbitrarily to 0 kcal·mol–1.
Energies are normalized to the composition of X–F in each case for comparison.
Z. Anorg. Allg. Chem. 0000, 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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T. Drews, K. Seppelt
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Physical Measurements: JEOL JNM-LA 400MHz multinuclear NMR
spectrometer, 1403 Spex industries Raman spectrometer with
1064 nm / 300 mW laser excitation, Bruker SMART CCD 1000 TK
diffractometer with Mo-Kα irradiation and graphite monochromator,
ω-scan method.
Bromine Fluoride: Usually Br2 (10–20 mg) was dissolved in solvent
(2 mL) in a 5 mm NMR tube and cooled to –100 °C. C2H5–CN,
CH2Cl2, CH3Cl dissolve Br2 completely, also the CH3–CN/CH2Cl2
mixture. Suspensions of finely divided Br2 in C2H5F and CH3F were
obtained by dissolving similar amounts at –30 °C (C2H5F) of –60 °C
(CH3F) in closed tubes (caution, high pressure!) and shock frozen to
–196 °C. 20% F2 in N2 was passed through a NaF column in order to
free it from residual HF and afterwards bubbled into the solutions by
a PFA capillary (PFA = perfluorovinyl ether tetrafluoro ethylene co-
polymerisate). The orange color of the bromine solutions lightened up
to yellow, and in those cases where the Br2 was only partially dis-
solved, it slowly went into solution. In these cases the fluorination was
stopped when a small residue of solid bromine was left in order to
avoid over-fluorination. Usually the fluorination lasted 45 min at a
speed of 1 gas bubble per second through a 1 mm thick PFA capillary.
During the fluorination the temperature was held between –95 °C and
–110 °C. The samples were transferred without warming into the NMR
and Raman spectrometer.
Figure 6. Calculated structures /pm,° and energetics (a.u., zero point
energy corrected, MP2 approximation) of some Br–F systems.
Crystal Growth and X-ray Measurement: A solution of BrF in
CH3Cl was prepared as described. The solvent was reduced by evapo-
ration at –120 °C to about 10% of its volume. Subsequently, CH2ClF
(1 mL) was added. This mixture was slowly cooled to –140 °C when
orange crystals appeared. With a special device modified[27] one crys-
tal was mounted on a glass capillary and glued on it by a perfluoro-
hexane/perfluoro vinylether oil. 1800 frames by 0.3° scans in ω were
taken, 20 sec per frame, covering a full sphere of reflections, followed
by semi empirical absorption correction by equalizing symmetry
equivalent reflections (method SADABS). The structure was solved
and refined by the Sheldrick programs[28] (for details see Table 4).
spectra. The Br–F stretching region is always disturbed by the
presence of BrF3, whose Raman absorptions vary very much
with concentration, temperature, and solvent. The three defor-
mation modes of Br–BrF2 may be characteristic but are pre-
dicted to be weaker in the Raman spectrum, and none of them
can be located with certainty (Table 3).
The analogue Cl–ClF2 is predicted to be quite unstable, on
the contrary I–IF2 could be quite stable, similar to IF3 that has
be isolated.[6] The possible dimerization of BrF into Br–BrF2
is paralleled by the experimentally established dimerization of
SF2 into F–S–SF3.[26]
Bromine Chloride: Bromine (50 mg) was dissolved in CH2Cl2
(3 mL). With a glass vacuum line an excess of Cl2 was condensed into
the glass ampoule, and the ampoule was sealed. Warming to room
temperature und shaking the content, followed by slowly cooling to
–78 °C overnight, afforded orange crystals. The crystallographic pro-
cedure was done as above.
Conclusions
BrF can be prepared, but it is very unstable. The question
of its solid-state structure remains open. Another interesting
case is that of IF. A similar approach for its preparation seems
impossible so long as no suitable solvent for I2 at –100 °C or
below is found.
Computational Procedure: The ab initio and DFT calculations were
performed with the Gaussian 03 programs[29] using the implemented
MP2, MP4, CCSD(T), and Becke3LYP procedures as implemented in
the program. Basis sets: Cl, F: aug-cc-pVTZ as implemented in the
program, Br: Relativistically corrected core potential for 28 electrons
and a 14s10p2d1f(3s3p2d1f) basis set, I: Relativistically corrected core
potential for 28 electrons and a 22s21p10d2f(6s5p4d2f) basis set.[30]
Experimental Section
Caution: Handling 20% F2 in N2 requires rigorous safety protections.
In the majority of the calculations we used the MP2 approximation,
Materials: 20% F2 in N2 was provided by Solvay Co, Bad Wimpfen, since it is known that this method is able to reproduce weak interac-
Germany. All used solvents were treated before use with 20% F2 in
N2 at –100 °C.
tions better than the more economical DFT methods, although it might
overestimate all bond strengths. More precise thermodynamic data
Table 3. Calculated vibrational spectra of Br–BrF2 /cm–1 (Raman intensity).
νasBrF2, B2
νsBrF2, A1
νBrBr, A1
τBrF2, B1
δsBrF2, A1
δasBrF2, B2
CCSD(T)
MP4
581
564
527
500
310
308
255
246
2001
184
184
178
MP2
B3LYP
593(0.9)
560(0.9)
530(42.8)
512(31.0)
329(7.5)
296(8.3)
255(0.0)
254(0.0)
202(2.7)
180(4.0)
187(3.8)
177(4.0)
4
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Bromine Monofluoride
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[16] We tentatively explain the kinetic instability of CH2ClF against
F2(N2(1:4) at –100 °C as follows: F2 is very insoluble in CH2Cl2,
so only a slow reaction occurs. F2 is better soluble in CH2F2, but
the further fluorination to CHF3 or CF4 is kinetically (higher posi-
tive charge on the hydrogen atoms) and thermodynamically hin-
dered. In CH2ClF there might be higher solubility of F2 along
with a quicker and more exothermic reaction.
Table 4. Crystallographic data of BrF·CH3Cl and BrCl (ordered modi-
fication).
BrF·CH3Cl
BrCl
M
149.4
115.4
T /°C
–150
–140
Space group
a /pm
b /pm
Pnma (No 62)
945.9(2)
655.8(3)
692.6(1)
429.7
Cmc21 (No 36)
644.9(3)
454.7(2)
835.0(3)
244.9
c /pm
V /106pm3
Z
4
4
ρ calcd
2.310
3.129
Reflections
Collected
Independent
2θmax /°
μ /mm–1
Rint
R refined parameters
wR2
R [Fo Ͼ 4σ(Fo)]
5231
706
61.04
10.0
0.0248
32
0.0470
0.0191
1476
404
61.00
17.44
0.0199
14
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84–89.
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Chem. Eur. J. 2004, 10, 6565–6574.
0.1233
0.0450
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[21] P. Hansen, S. Brodersen, G. Guelachvili, J. Mol. Spectrosc. 1981,
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would be obtained by the CCSD(T) method, but these calculation ex-
ceeds our available computer resources at least for the larger systems.
[22] R. Boese, A. D. Boese, D. Bläser, M. Y. Antipin, A. Ellern, K.
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Further details of the crystal structure investigations may be obtained
from the Fachinformationszentrum Karlsruhe, 76344 Eggenstein-
Leopoldshafen, Germany (Fax: +49-7247-808-666; E-Mail:
crysdata@fiz-karlsruhe.de, http://www.fiz-karlsruhe.de/request for de-
posited data.html) on quoting the depository number CSD-424851
(BrF–CH3Cl) and CSD-424850 (BrCl).
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Acknowledgements
[27] H. Schumann, W. Genthe, E. Hahn, M.-B. Hossein, D. v. d. Helm,
J. Organomet. Chem. 1986, 298–317, 2561–2567.
This work was supported by the Deutsche Forschungsgemeinschaft as
part of the Graduiertenkolleg “Fluorine as a key Element“ DFG GK
1582/1.
[28] G. M. Sheldrick, Acta Crystallogr., Sect. A 2008, 64, 112–122.
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Received: June 25, 2012
Published Online: ᭿
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Date: 07-08-12 17:07:24
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T. Drews, K. Seppelt
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Bromine Monofluoride
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