A 9F nuclear magnetic resonance and Raman spectroscopic investigation of

the reaction of iodine oxide pentafluoride with the Lewis acids,

antimony and arsenic pentafluoride
MORLEY
BROWNSTEIN,
RONALD A N D JOHNP. KRASZNAI
J. GILLESPIE,
Depnrtrnenf of Cltc~misfry,McMrrsfer University, Hrrrnilfon, Ottf., Crrnndrr L8S4Ml
Received September 20, 1977

MORLEY BROWNSTEIN, RONALDJ. GILLESPIE, and JOHNP. KRASZNAI. Can. J. Chem. 56,
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 189.169.56.173 on 05/31/16

2253 (1978).
The reactions of IOF, with SbF, and with AsF, have been investigated at low temperature
by I9F nmr and Raman spectroscopy. It was found that SbF, forms labile 1 : 1 and 2 : 1 com-
plexes whereas AsF, forms only a 1 : 1 complex. The IOF, is bound through its oxygen atom
to the Lewis acids AsF,, SbF,, or (SbF5)Z.

MORLEY BROWNSTEIN, RONALD J. GILLESPIE et JOHNP. KRASZNAI. Can. J. Chem. 56,2253

(1 978).
Les rCactions entre IOF, et SbF, ou AsF, ont Cte CtudiCes a basse tempirature par spectros-
copie rmn (19F) et Raman. Dans le cas de l'antimoine la formation de complexes labiles 1 : 1
et 2 : 1 a CtC mise en evidence. Par contre avec l'arsenic seul le complexe 1 : 1 se forme. Le ]OF5
est lit par son atome d'oxygene aux acides de Lewis AsF,, SbF, ou (SbF5)z.

Introduction
For personal use only.

It has been shown by Bartlett and Beaton (1) that

IOF, does not react with SbF, even at elevated
temperature and pressure to give the IOF,+ cation.
We have used I9F nmr and laser Raman spectros-
copy to investigate the interaction of IOF, with SbF,
and AsF, and we have obtained evidence for the
formation of donor-acceptor complexes in which
the Lewis acid is coordinated to the oxygen of IOF,.
Similar complexes have been observed previously
(2, 3) between SbF, or AsF, and weak bases such as
SO,ClF, SOF,, CH3S02F, and SO, and it was
shown that in all of these complexes the base is co-
ordinated to the Lewis acid via the oxygen. SO,F,,
on the other hand, was found to be too weak a base
to interact with SbF, or AsF, even at very low
temperatures and, hence, it was used as an inert low
temperature solvent for the present work.
Results and Discussion
The IOF,-AsF, System
The room temperature I9F nmr spectrum of a
solution of IOF, and excess AsF, in S 0 2 F 2shows in
addition to the solvent peak a very broad line with a
linewidth at half height of 1040 Hz at 61 ppm upfield
from external CFCl, which can be assigned to the
F-on-As resonance and a rather broad and weak
peak at - 66 ppm which can be assigned to IOF,. As
the sample is cooled to - 11O0C,the F-on-As reson-
ance sharpens and the previously collapsed spectrum
of IOF, becomes well resolved to give a second
order AB, multiplet. Figure 1 shows the spectrum of
a solution containing IOF, and excess AsF, in
SO,F, at - 110°C, and Table 1 lists the nmr param-
Ho(p.p.m, from CFCI3) -
Frc. 1. The 19Fnmr spectrum of a solution of IOF, and
excess AsF, in S02F2(S)at - 110°C; *, change in spectrom-
eter gain.
eters. The AB, multiplet of the IOF, spectrum
shows all nine of the expected transitions (4) for the
A spin system. The second order transitions for the
B spin system are not observed because the lines are
rather broad and the linewidth is comparable with
the expected separation of the lines. The AB,
spectrum differs from that of a solution of IOF, in
SO,F, (Fig. 2) in both chemical shift and F-F
coupling constant and the linewidth is reduced from
180 to 50 Hz in the presence of AsF,. These observa-
tions suggest that there is complex formation between
IOF, and AsF, at these low temperatures. This
complex formation is responsible for the change in
the chemical shift and coupling constant of IOF, and
it also increases the rate of quadrupole relaxation of
the iodine by making the electric field gradient
around the iodine nucleus less symmetrical and thus
 C A N . J . CHEM. VOL. 56. 1978

TABLE1. Chemical shifts (ppm from CFCI,) and coupling constants J (Hz) for the
IOF, :AsF, : S 0 2 F 2 system

IOFs AsF,

Temp. ("C) IOF, :AsF, A B4 J" Shift Widthh

+26 1:5 n.0.' - 66.3 n.0. 60.9 1040

-110 1:5 -96.8 -65.9 253 57.9 220
-110 1: O d -106.9 -69.1 271 - -
"Coupling constant obtained by comparison with theoretical AB, spectra (ref. 4).
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 189.169.56.173 on 05/31/16

bLinewidth at half height.

=Under these conditions, neither the peak A nor the fine structure of peak B are observed.
dSolution of IOFS in SO2F2(see Fig. 2).

greater for complexed AsF, than for uncomplexed

AsF, giving rise t o a sharper line for the former.
The Raman spectrum of the I : I adduct is shown
in Fig. 3A and Table 2 lists the frequencies and
approximate descriptions of some of the vibrational
modes for both the AsF, and SbF, adducts, together
with pure IOF,, AsF,, and SbF, at - 100°C. The
IOF, group of the complex retains C4, symmetry o n
the nmr time scale in S02F2 solution at - 100°C.
However, this symmetry is probably lowered in the
solid and since there are 13 atoms in the complex, a
For personal use only.

maximum of 33 fundamental modes are expected in

the vibrational spectrum. Clearly it is not possible t o
assign all of these peaks with certainty but since the
I=O stretching mode has the highest frequency in
free IOF, we can at least assign the I 0 stretch in the
complex with confidence. The peak at 921 cm-' is
the I 0 stretch of free IOF, (5, 6) which is produced
by partial dissociation of the complex: (eq. [I])

HO ( p p m . from CFC13)-
FIG.2. The "F nmr spectrum of a solution of IOF, in
SO2F2(S) at - 110°C; *, change in spectrometer gain.
decreasing the linewidths. Similarly, the sharpness
of the F-on-As peak indicates a much greater rate
of quadrupole relaxation of the 7 5 ~(Is = 3) nucleus
than in AsF, alone. This would be expected since the
electric field gradient about the arsenic will be greater
in the complexed molecule than in uncomplexed
AsF,. Although free AsF, has a trigonal bipyramidal
structure, very rapid intramolecular exchange of the
fluorine atoms (pseudorotation) causes a rapid
averaging of the electric field gradient to a low value.
This very much decreases the rate of quadrupole
relaxation and an extensively but incompletely
collapsed multiplet spectrum is observed as a rather
broad single line. In complexed AsF,, although there
is apparently a more symmetric octahedral arrange-
ment of bonds about arsenic, five are strong As-F
bonds while the sixth is a weak As-0 bond. The
resultant electric field gradient and, hence, the rate
of quadrupole relaxation would be expected to be
The intensity of this peak increases at the expense of
the peak at 853 cm-' as the temperature is raised
from - 100°C and, therefore, we assign the peak at
853 cm-' to the I 0 stretch of the complexed IOF,.
The reduction in the I 0 stretching frequency o n
complexation is consistent with a contribution from
a single bonded resonance structure 2 to the structure
of the complex. A separate AB, spectrum is not
observed for the uncomplexed IOF, and since the
peaks of the complex are reasonably sharp we con-
clude that even a t - 100°C there is fast exchange
between the complex and its components. A similar
observation was made in the SOF,-AsF, system (3)
where at - 100°C only one sharp peak was observed
in the F-on-S region of the nmr spectrum. The A s 0
stretching frequency is difficult t o assign due to the
 BROWNSTEIN ET AL. 2255

J
A complexity of the Raman spectrum but in the ions
AsF,OH- and AsF,(OH),- it has been found a t
562 and 554 cm-' respectively (7). However, in the
spectrum of the adduct no peaks are observed
between 500 and 600cm-'. The 10 stretching
frequency of 853 cm-' indicates considerable double
bond character in the I 0 bond as the frequency is
close t o that of 104- (838 cm-') (8). Hence, one
I I I 1 might expect that the A s 0 bond will b e correspond-
I
dm sm ebo I
sm & 4bo XU m~ ingly weak. Therefore, we tentatively assign the peak
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 189.169.56.173 on 05/31/16

at 438 cm-' to the A s 0 stretching frequency.

pJ
The IOF,-SbF, System
The room temperature 19F nmr spectrum of
solutions of IOF, a n d SbF, in SO,F, as solvent
exhibit very broad lines for the F-on-I(VI1) and
F-on-Sb(V) regions of the spectrum. However, o n
cooling the solution t o about - 100°C fine structure
is observed. Figure 4 shows the spectrum of a n
equimolar solution of IOF, and SbF, in S 0 2 F 2 a t
- 110°C and the various parameters derived from
the spectrum are summarized in Table 3. The
spectrum shows in addition to the solvent peak, S,
For personal use only.

several complex multiplets in the F-on-I(VI1) and

> F-on-Sb(V) regions.
t We interpret the spectrum in terms of free IOF,
cn
Z and 1 :1 and 1 : 2 IOF,-SbF, complexes 3 and 4.
W
F
5

FF(+
T
01F5
3

FI
F2
cis

FZL F 3

F1
/ ;/F2 QowsF4
F2
trans
4
9 o 0 ~ ~ ~ ) ~ o o 6 o o m m m m 1Furthermore,
oo the spectrum is only consistent with
Au, cm-' the IOF, coordinating t o SbF, through oxygen and
FIG.3. Raman spectra of: (A) IOF5.AsF5at - 100°C; (B) not through fluorine. The five fluorines on Sb in
; IOF5.2.2SbF5 at - 8 3 0 ~ ; ( D ) structure 3 are expected to give rise t o an AX4
IOF,.S~F, at - 1 0 0 ~ ~(c)
IOF5.2.2SbF5at 25°C. spectrum as observed for the multiplets labelled G.
 C A N . J. CHEM. VOL. 56. 1978

TABLE2. Raman spectra of IOF5.MF5 complexes and AsF,, IOF,, and SbF,

IOF5.AsF5" IOF, :s ~ F , " IOF5.SbFSeJ

(1 : 1) AsFSb~'l IOF," S bFScJ (1 : 1) (1:2.2) Assignment

920(19)p I = 0 str. (free IOF,)

873(9)~ I = 0 str. (1 :2 complex)
- I = 0 str. (I : 1 complex)
757(4)dp
-
-
-
Can. J. Chem. Downloaded from www.nrcresearchpress.com by 189.169.56.173 on 05/31/16

703(57)p
-
-
-
-
678(100)p
-
-
652(64)p
637(42)p
608(6)dp

439(4)~ (As)Sb-.O str.

-
-
373(sh)dp
For personal use only.

-
360(14)dp
340(14)dp
-
321(12)dp
-
298(10)dp
- 292(10)dp
268(m) 265(10)dp
24 1(m) 245(7) ?
231(7)dp
21 l(7)dp
145(7)~
126(5)~
T h i s work. Spectrum recorded at -100°C.
bGG. J. Schrobilgen, unpublished work (solid spectrum).
<Reference 16.
dReference 17. Infrared spectrum.
=Left-hand column refers to spectrum at -83'C, right-hand column at room temperature.
f p = polarised, dp = depolarised, m = medium, vs = very strong, w = weak.

Ho (p p m from CFC13 ) -
FIG.4. The 19Fnmr spectrum of a solution of IOFs.SbFs in S02F2(S) at - 110°C; *,change in spectrometer gain. The
region of the spectrum between -80 and - 115 ppm is shown in detail.
 BROWNSTEIN ET AL.
3. I9F nmr parameters" for an equimolar mixture of IOF, and SbF5 in S 0 2 F 2at - 110°C
TABLE
F-on-I (VI I)
A B4 J F1
IOF5.2SbF5 -91.2 -71.2 257 146.1
A B4 J A
IOF5.SbF5 -94.0 -68.7 278 146.1
A B4 J
Uncomplexed
IOF5 - 106.7 n . ~ . ~271
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'Chemical shifts (ppm from CFCI,) converted from S 0 2 F Zinternal reference (Ss02F2= SCFCI,
*B spin system for uncomplexed IOFS IS obscured by those o f the I : I a n d 1 :2 complexes.
The fluorines F2 in the cis bridged structure 4 are
expected to be the most intense part of the spectrum
for this complex and to be a doublet of doublets from
coupling to both F , and F, and therefore M is
assigned to fluorines F,. Double resonance experi-
ments by Dean and Gillespie (2) for the S0,CIF-
SbF, system where the profile of the Sb region is
very similar to that in the IOF,-SbF, system showed
that the peaks labelled K, L, N, 0 , and P may be
assigned to the fluorines F,, F,, F,, F,, and F,,
respectively. F3 is coupled to fluorines F,, F,, F,,
For personal use only.
and perhaps F6 and is, therefore, expected to give
rise to a broad unresolved line as seen for resonance
K. F, is expected to be a quintet provided J,,-,, is
zero as in Sb,F,,- (9) by coupling to the four
equivalent fluorines F,. The fluorines F,, F,, and F6
are expected to give rise to complex multiplets by
coupling to F, and with each other. There is no
evidence from the l g F nmr spectrum for the trans
bridged structure although the Sb,F, ,-
anion, which
is isoelectronic with the 1: 2 complex, has been
shown (10) to be cis bridged in solution and trans
fluorine bridged in the solid (1 1).
In the F-on-I(VI1) region, we assign the second
order AB, multiplet to the fluorines on iodine in the
1 : 1 complex and the A'B', multiplet to those in the
1 : 2 complex; the approximate ratio of the inten-
sities of AB4:AfB', is 1:0.5 which is in excellent
agreement with the approximate intensities of the
resonances in the F-on-Sb region which give a mole
ratio of 3 :4 = 1 :0.5. However, since the original
solution was equimolar in IOF, and SbF,, the
presence of 4 indicates that there must also be some
free IOF, in the solution. The two broad weak lines
at - 106.7 and - 1 12 ppm (A") are assigned to two
transitions of the A spin system of free IOF,
(A"Bf',), the remaining lines being hidden under
the A and A' resonances whilst the B" doublet of
free IOF, is hidden under the B and B' doublets of
the 1 : 1 and 1 :2 complexes (Fig. 4).
The Raman spectra of an equimolar mixture of
IOF, and SbF, as well as a mixture with excess SbF,
were recorded at low temperature in the absence of a
2257
F-on-Sb(V)
F2 F3 F4 F5 F.5 JF,-F~ JF*-F,
114.9 87.2 134.5 97.2 127.3 90 49
x4 J
106.9 91
+ 32.04 ppm) coupling constants ( J ) i n Hz.
solvent (Fig. 3B, C, D). The I 0 region of the spec-
trum showed three peaks for the equimolar solution
but only two for the solution containing excess SbF,.
The peak at 918 cm- ' can be unambiguously assigned
to the I 0 stretch of free IOF, (5, 6) and the peaks
at 872 and 864 cm-' to the 1 : 2 and 1 : 1 complexes
of IOF, with SbF, respectively. The nmr spectrum
of an equimolar solution in SO,F, showed that the
1: 1 complex was present in higher concentration
than the 1 : 2 complex at low temperature and this
formed the basis for the assignment of the more
intense peak at 864 cm- ' to the 1 : 1 complex and the
shoulder at 872 cm-' to the 1 : 2 complex. For the
sample which contained excess SbF,, the Raman
spectrum at - 83OC showed only the peaks attribut-
able to the complexes, i.e. at 858 and 875 cm-'. As
this solution was warmed the peak at 875 cm-'
increased in intensity at the expense of the one a t
858 cm-' and dissociation to free IOF, occurred as
evidenced by the appearance of the peak at 920 cm-'.
At room temperature the peak at 858cm-' had
disappeared completely. This dissociation can be
expressed by [2].
[21 210F5.SbF5 IOF5.2SbF5 + I O F 5
At low temperature there is an appreciable quantity
of the 1 : 1 complex which dissociates until at room
temperature the equilibrium lies predominantly t o
the right. The shift of the I 0 stretching mode t o
lower frequency is consistent with complexation
through the oxygen and, furthermore, the shift of
about 60 cm-' indicates a relatively weak inter-
action. The SbO stretching mode is found at a
frequency of 553 cm-' in SbF,(OH)- (7) and for
the same reasons as were discussed earlier for the
AsF, complex, we assign the polarised band at
438 cm-' in the SbF, adduct to the SbO stretching
frequency. However, if two different I 0 stretches are
observed for the I : I and 1 :2 complexes then two
separate SbO stretches should also be observed. The
position of the peak at 438 cm-' does not change as
the sample is warmed to room temperature and we
must conclude that the two SbO stretching fre-
 2258 CAN. J. CHEM. VOL. 56, 1978
quencies for the 1 : I and 1 :2 complexes are co-
incident. These assignments should, however, be
regarded as tentative since in practice it is very
difficult to distinguish between SbF, IF, and SbO
stretching frequencies in complex molecules such as
these.
Conclusions
SbF, forms 1: 1 and 2 : 1 complexes with IOF,.
Because AsF, shows very little tendency to form
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polymeric As,,F,,, units, it forms only a 1 : 1 adduct.
In all of these complexes the IOF, is oxygen bridged
to the Lewis acid. This bridge in the 2 : 1 complex is
shown to be cis to the fluorine bridge of the Sb,F,,
unit. Since both the 1 : 1 and 2: 1 complexes exist in
solution together with uncomplexed IOF,, the Lewis
basicity of the 1 : 1 complex must be comparable to
that of IOF, itself.
It is interesting that IOF, is not a fluoride ion
donor whereas IF, loses a fluoride to a strong Lewis
acid such as SbF, to give the IF,' cation. Christe
has pointed out that highly symmetrical (i.e., octa-
hedral and tetrahedral) fluorides and oxyfluorides
For personal use only.
(1 5)- are frequently poorer fluoride ion donors than
similar compounds of lower symmetry.
'\
Experimental
Preporrrtiot~of IOF,
IOF, was prepared by the partial hydrolysis (12) of IF, in a
Kel-F trap containing a small amount of sodium fluoride to
remove the H F produced.
IF, was prepared by the high pressure, high temperature
fluorination (13, 14) of iodine pentafluoride (Matheson) in a
welded Monel can connected via &in. Monel tubing to a
Monel vacuum line. Excess fluorine was removed by pumping
the vessel at - 196°C.
Antimony pentafluoride was obtained from the Ozark
Mahoning Co., and triply distilled in an atmosphere of dry
air using an all-glass apparatus.
Arsenic pentafluoride was obtained from the Ozark Mahon-
ing Co., and used directly.
Sulfuryl fluoride (Matheson of Canada) showed only one
line in the "F nmr spectrum and was used without further
purification.
N~~cleorMogt~eticResonat~ceMeosuretnet~ts
Fluorine nmr spectra were measured using a Varian
DA-601L spectrometer operating at 58.3 MHz and modified
as described previously (2) t o record spectra from the first
upper side band in the field sweep unlock mode.
Romatr Spectra
Raman spectra were obtained using a Spex Industries Model
1400 spectrometer utilizing the 5145 A radiation from a
Spectra Physics model 164 argon ion laser. Spectra were
recorded at - 100°C by placing the sample tube inside a glass
tube surrounded by a n evacuated jacket, silvered except at the
centre. Liquid N, was boiled off from a Dewar flask a n d
passed through the tube. The temperature was monitored with
a copper-constantan thernlocouple positioned in the stream
just ahead of the sample region. T h e Raman shifts a r e
estimated to be accurate to f 2 cm-'.
S ~ t t ~ pPreporotiotz
le
All manipulations were carried o u t under anhydrous
conditions on a vacuum line constructed from Monel, Kel-F,
and Teflon or in a dry box. All preparative work was done in
15 cm x 2 cm od Kel-F tubes (Argonne National Laboratory)
equipped with Kel-F heads and Teflon valves.
The nmr and Raman samples were prepared and vacuum
sealed in 5 mm od medium wall Pyrex nmr tubes attached t o
Teflon valves with 2 in. Teflon nuts a n d ferrules. The SbF,
samples were prepared by distilling a n appropriate quantity
of IOF, onto a known amount of SbF, and then distilling in
an excess of SO,F,. The AsFS samples were prepared
sinlilarly except that the AsF, was distilled onto a known
amount of IOF, and then the solvent, S 0 2 F , , was added.
Acknowledgement
We thank the National Research Council of
Canada for financial support of this work.
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