Article

pubs.acs.org/JPCA

Gas-Phase Generation and Matrix Isolation of the Methylsulfonyl

Radical CH3SO2• from Allylmethylsulfone
Hans Peter Reisenauer,*,† Peter R. Schreiner,† Jaroslaw Romanski,‡ and Grzegorz Mloston*,‡
†
Institute of Organic Chemistry, Justus-Liebig University, Heinrich-Buff-Ring 58, D-35392 Giessen, Germany
‡
Department of Organic and Applied Chemistry, University of Lodz, Tamka 12, 91-493 Lodz, Poland
*
S Supporting Information

ABSTRACT: The atmospherically highly relevant methyl-

sulfonyl radical (CH3SO2•) was generated by high-vacuum
flash pyrolysis (HVFP) of allylmethylsulfone and isolated in an
argon matrix at 10 K; the allyl radical formed as the
cofragment. Upon thermolysis, the methylsulfonyl radical
undergoes partial decomposition, leading to substantial
amounts of sulfur dioxide in the matrix. The title compound
was characterized through the assignment of eight fundamental
IR bands of its CD3 and 13CH3 isotopologues and the excellent
agreement with the B3LYP/6-311+G(3df,3pd) computed
harmonic vibrational frequencies. The two most intense
absorptions were found at 1267.1 and 1067.6 cm−1. In
extension of this study S-methyl methanethiosulfonate was found to be another suitable, although less efficient, precursor for the
gas-phase generation of the methylsulfonyl radical.

■ INTRODUCTION
Sulfur-containing radicals derived from oxidation processes of
volatile sulfur organic compounds in the atmosphere have
extensively been investigated because of their relevance in the
multiple reaction pathways eventually leading to atmospheric
sulfate aerosols. These affect the earth’s radiation balance either
by direct backscattering of solar radiation or indirectly via the
cloud albedo by forming cloud condensation nuclei.1−5 Two
distinct representatives of this class of radicals species are the
methylsulfinyl (1) and methylsulfonyl radicals (2) (Scheme 1).
Scheme 1. Methylsulfinyl (1) and Methylsulfonyl Radicals
(2)
The formation of 1 and 2 in the atmosphere is believed to
occur via oxidation of dimethyl sulfide produced in large
amounts by biodegradation of phytoplankton present in the
oceans.1−5
Sulfonyl radicals (R−SO2•) are also widely applied as
versatile intermediates in organic synthesis, for example, for
the preparation of unsaturated sulfones,6−8 and as universal
leaving groups in reversible addition−fragmentation chain-
transfer polymerization.9 Particular attention focuses on 2, and
its spectroscopic properties were described in recently
published reports.6−8,10−17 ESR spectroscopy allowed the
detection of 2 as a radiolysis product of H2O/DMSO
mixtures.10 The IR frequencies of 2, generated through the
reaction of methyl radicals and sulfur dioxide, were reported for
the gas phase and for 2 isolated in para-hydrogen matrixes;
these compare favorably with computed values.11,12 Radical 2
was also identified as a short-lived intermediate in the pulse
radiolysis of methanesulfonyl chloride through its UV
absorption at λmax ≅ 320 nm.6−8,13 The structure and reactivity
of 2 were the subject of many theoretical studies at the density
functional theory (DFT) and ab initio (up to CCSD(T)/F12)
levels.11,12,14−17
In a recent paper, we reported an efficient method for the
generation and matrix isolation of 1 by high-vacuum flash
pyrolysis (HVFP) of allylmethylsulfide S-oxide (3).18 This
success prompted us to utilize an analogous protocol for the
generation of 2 from allylmethylsulfone (4) (Scheme 2).
The specific challenge of this strategy lies in the fact that the
C−S bond in 2 is very weak and the dissociation leading to the
methyl radical and sulfur dioxide can easily occur (Scheme 2).
Experimental and computational (B3LYP/aug-cc-pVTZ) esti-
mates provide a C-S bond dissociation energy (BDE) of only
about 14 kcal mol−1.12,16 Therefore, the subsequent dissociation
of the target radical 2 into sulfur dioxide and the methyl radical
is expected to proceed readily under the pyrolysis conditions,
whereas the comparable cleavage of 1 into the methyl radical
Special Issue: Markku Räsänen Festschrift
Received: April 14, 2014
Revised: May 24, 2014
Published: May 28, 2014

© 2014 American Chemical Society 2211 dx.doi.org/10.1021/jp5036647 | J. Phys. Chem. A 2015, 119, 2211−2216
The Journal of Physical Chemistry A
Scheme 2. B3LYP/6-311+G(3df,3pd) Assessment of the
Bond Dissociation Energies (BDEs) for the Formation of
the Methylsulfinyl (1) and Methylsulfonyl (2) Radicalsa
a
Values in kcal mol−1.
and SO requires much more energy (about 23 kcal mol−1) and
is thus very unlikely to occur. Moreover, our B3LYP/6-
311+G(3df,3pd) computations predict that the energy required
for splitting off the allyl radical from the S,S-dioxide 4 is 16.2
kcal mol−1 higher than that for the same process for S-
monoxide 3.
■
EXPERIMENTAL SECTION
Preparation of the Precursor. The preparation of 4 and
its isotopologues was based on known proctocols.19−22 A
solution of ally1 bromide (1.94 g, 0.016 mol) and thiourea (1.0
g, 0.016 mol) in methanol (20 mL) was refluxed for 1 h, and
then, after addition of a methanolic solution of NaOH (1.28 g
in 15 mL), heating was continued for another hour. Next, the
solution was cooled to −10 °C, and MeI (2.28 g, 0.016 mol)
was added in small portions. The mixture obtained thereby was
refluxed for the next 0.5 h. After this time, the mixture was
distilled, and the allylmethylsulfide was collected as an
azeotrope with methanol (bp 62−64 °C). A solution of
allylmethylsulfide (1.0 g, 11.0 mmol) in glacial acetic acid (3
cm3) was chilled in ice, and the 30% aq hydrogen peroxide (2
or 3 times excess) was added dropwise, and the mixture was
stirred overnight. The solution was heated at 85 °C for 1 h,
then cooled, and diluted with an equal volume of water. The
aqueous solution was extracted twice with methylene chloride.
The combined organic layers were washed with water and dried
over anhydrous MgSO4. The solvents were evaporated under
reduced pressure, and the residue was distilled at 120 °C/0.1
mm Hg (Kugelrohr) to yield 0.8 g of product. Because traces of
allylmethylsulfoxide could not be removed by distillation,
preparative GC was applied to get the necessary amounts of
pure sulfone 4 for the matrix experiments. Commercially
available S-methyl methanethiosulfonate (5) was used without
further purification.
Matrix Isolation Experiments. The cryostat used for the
matrix isolation studies was an APD Cryogenics HC-2 closed-
cycle refrigerator system fitted with CsI windows for IR and
BaF2 windows for UV/vis measurements. IR spectra were
recorded with a Bruker IFS 55 FTIR spectrometer (4500−300
cm−1; resolution: 0.7 cm−1), and UV/vis spectra were recorded
with a JASCO V-670 spectrophotometer (spectral range: 190−
2500 nm; resolution: ≥ 0.1 nm). We employed a small home-
built water-cooled oven directly connected to the vacuum
shroud of the cryostat for the combination of HVFP with
matrix isolation. The pyrolysis zone consisted of an empty
quartz tube (inner diameter, 8 mm; length of heating zone, 50
mm) resistively heated by a coax heating wire; the temperature
was controlled by a Ni/CrNi thermocouple. The precursors
were evaporated from a cooled storage bulb (allylmethylsulfone
2212
Article
(4): −6 °C; S-methyl methanethiosulfonate (5): −25 °C) into
the pyrolysis tube. Immediately after leaving the tube, at a
distance of ∼50 mm, the pyrolysis products were co-condensed
with a large excess of argon on the surface of the 10 K cold
matrix window during a time of 2−4 h. Pyrolysis temperatures
were varied between 500 and 900 °C; the optimal temperatures
with respect to the yields of methylsulfonyl radicals (2) were
800 (4) and 850 °C (3). For irradiations, a mercury high-
pressure lamp (Osram, HBO 200 in connection with a Bausch
& Lomb monochromator; slits set to a spectral half-width of
Δλ = 10 nm) was used. An unspecific photodegradation of 2 to
COS, CO, H2S, and H2O was observed with λ = 313 nm (7 h
for complete conversion). Subtraction of the corresponding
spectra before and after photodegradation was made to extract
the IR and UV/vis spectra of 2. The same procedure was
applied for the CD3 and 13C isotopologues.
■ COMPUTATIONAL METHODS
We utilized DFT to assess reaction energies and equilibrium
geometries, harmonic vibrational wavenumbers, as well as IR
intensities of all key structures using the B3LYP23,24 functional
with a large basis set including polarization and diffuse
functions (6-311+G(3df,3pd)) as implemented in the GAUS-
SIAN 09 program.25 All stationary structures were characterized
as minima or transition structures by computing analytical
harmonic vibrational frequencies (cf. the Suppporting In-
formation (SI)).
■ RESULTS AND DISCUSSION
Allylmethylsulfone (4) can readily be prepared through the
sequence of reactions depicted in Scheme 3.19−22
Scheme 3. Two-Step Synthesis of Allylmethylsulfone (4)
The parent compound and its CD3 and 13CH3 isotopologues
were prepared by treatment of sodium allylthiolate with CH3I,
CD3I, and 13CH3I, respectively, and were oxidized with an
access of H2O2 in glacial acetic acid. Distillation yielded
colorless oils that were used for HVFP experiments. Reaction
conditions were optimized with respect to a maximum yield of
2 by several test runs and eventually established 800 °C at
∼10−5 mbar as the optimal temperature and pressure. The
pyrolysate was condensed with a large excess of argon at 10 K
on the surface of the spectroscopic window to form a solid
matrix, which subsequently was analyzed by means of IR and
UV/vis spectroscopy. The IR spectrum (Figure 1) revealed the
presence of strong absorption bands at 1535/1531, 1151/1147,
and 519/517 cm−1, which could easily be attributed to sulfur
dioxide (SO2) by comparison with an argon matrix spectrum of
a pure sample.
Another set of absorption bands located at 801, 984, 1389,
and 1477 cm−1 provides evidence for the presence of the allyl
radical formed as a coproduct of the thermal decomposition of
4.26−29 Finally, the presence of a set of narrow bands of
medium intensity at 1413.8, 1267.1, 1067.6, 631.3, 460.1, and
385.5 cm−1 shows the formation of 2 (Figure 2, Table 1). The
first four values correspond well with the recently reported IR
data of matrix-isolated 2 in solid para-hydrogen.11 The overall
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The Journal of Physical Chemistry A Article

Figure 1. FT-IR spectrum of the matrix-isolated pyrolysis products of allylmethylsulfone (4) (Ar, 10 K; pyrolysis temperature: 800 °C). Bands
attributed to the allyl radical are marked with an asterisk (∗).

Figure 2. (A) Computed (B3LYP/6-311+G(3df,3pd)) and (B) experimental (matrix-isolated, Ar, 10 K, bottom) IR spectrum of the CH3SO2•
radical. The experimental spectrum is a difference of the spectra taken before and after 5 h of irradiation with 313 nm. Bands attributed to the allyl
radical are marked with asterisks (∗).

observed spectral pattern fits nicely to the DFT-computed IR
spectrum of 2. With the aid of the computations, the additional
two weak low-frequency bands found at 460.1 and 385.5 cm−1
could be assigned to the (OSO) bending and to the SO2
wagging mode, respectively (Figure 2). Moreover, the
experimentally observed spectral band shifts upon deuteration
and 13C substitution of the methyl group agree well with the
values computed within the harmonic approximation (Table 1).
The presence of SO2, methyl radical, allyl radical, and 2
demonstrates that the thermal decomposition of 4 led to the
2213
expected products. However, as apparent from the spectrum in
Figure 1, a significant amount of unconverted 4 was also
present. This observation confirms the computational pre-
diction that the BDE for the C−S bond in 4 is 16 kcal mol−1
higher than that of 3.
Note that apart from the allyl and methylsulfonyl radicals,
also methyl radicals and sulfur dioxide (SO2) formed apparently
via secondary fragmentation of 2 in the gas phase. According to
our computations, the S−C BDE of 2 only amounts to 14 kcal
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The Journal of Physical Chemistry A Article

Table 1. Computed and Experimental IR Spectra of CH3SO2• (2) and Band Shifts for the 13CH3SO2 (13C-2), and CD3SO2• (d3-
2) Radicalsa
CH3SO2• (2) 13
CH3SO2• (13C-2) CD3SO2• (d3-2)
−1 −1
band position [cm ] band shifts [cm ] band shifts [cm−1]
sym. approx. mode comput. expt. comput. expt. comput. expt.
ν10, a″ CH str. 3185.1 (0.0) n.o. −12.2 n.o. −819.4 n.o.
ν1, a′ CH str. 3164.2 (0.5) n.o. −11.8 n.o. −817.1 n.o.
ν2, a′ CH str. 3060.6 (0.2) n.o. −12.4 n.o. −873.2 n.o.
ν3, a′ CH3 def. 1455.3 (9.7) 1413.9 (w) −2.6 −2.3 −402.9 −382.5
ν11, a″ CH3 def. 1446.8 (5.1) n.o. −2.5 n.o. −401.0 n.o.
ν4, a′ CH3 def. 1312.3 (0.9) n.o. −7.3 n.o. −312.0 n.o.
ν12, a″ SO2 str. 1271.1 (141.4) (34S: 1254.7) 1267.1 (vs) (34S: 1251.2) 0.0 0.0 −0.4 +0.3
ν5, a′ SO2 str. 1076.4 (66.1) (34S: 1069.2) 1067.6 (s) (34S: 1060.7) 0.0 −3.2 +1.2 +5.1
ν13, a″ CH3 rock. 955.5 (0.0) n.o. −7.1 n.o. −214.7 n.o.
ν6, a′ CH3 rock. 933.8 (6.8) 915.8 (w) −6.1 −5.7 −200.9 −189.0
ν7, a′ CS str. 624.8 (16.2) 631.4 (w) −12.1 −11.4 −28.3 −28.1
ν8, a′ SO2 def. 459.2 (15.7) 460.1 (w) −1.2 −1.1 −9.4 −9.0
ν9, a′ SO2 wag. 380.9 (21.3) 385.5 (w) −2.6 −2.1 −23.6 −25.2
ν14, a″ SO2 rock. 302.1 (0.1) n.o. −3.7 n.o. −26.1 n.o.
ν15, a″ CH3 twist. 173.5 (0.1) n.o. 0.0 n.o. −47.1 n.o.
a
Computations: UB3LYP/6-311+G(3df,3pd), harmonic approximation, unscaled frequencies; experiment: argon matrix, 10 K. Intensities (in
parentheses): in km mol−1 for the computations; approximate relative intensities (w: weak, s: strong, vs: very strong) of the experiments; n.o. = not
observed.

mol−1, and dissociation is expected in the gas phase before
trapping in the argon matrix.
The UV/vis spectra of the matrix-isolated pyrolysate exhibit
the known absorption bands of the allyl radical,26 which overlap
with additional broad absorptions located between 300 and 450
nm and originating from SO2 and 2 (Figure 3). Upon
Figure 3. UV/vis spectra of the matrix-isolated pyrolysate of
allylmethylsulfone (3). Solid line: not irradiated; dashed line: after 5
h of irradiation with 313 nm light.
photolysis using 312 nm light (mercury high-pressure lamp
with a monochromator), the broad absorption in the UV
spectral region between 300 and 450 nm disappeared, while the
characteristic absorption bands of the allyl radical were
unchanged (Figure 3). A difference spectrum taken before
and after photolysis shows a broad absorption band with a
maximum at around 340 nm (cf. SI) that is very similar to the
spectrum of 2 in solution.6−8,13
Along with the UV/vis spectra, a corresponding IR analysis
was performed to monitor the course of photolysis. A mixture
of COS, CO, and H2O was identified based on their specific IR
absorption bands. Although the photolysis of 2 led to a rather
unspecific decomposition, it proved to be very helpful in its IR
analysis through calculating meaningful difference spectra
(Figure 2).
Another precursor of 2 tested in the present study was S-
methyl methanethiosulfonate (5), which was expected to give 2
along with the mercaptomethyl radical (CH3S•) (6)30 via
homolytic cleavage of the S−S bond, although concerted
elimination of thioformaldehyde yielding methanesulfinic acid
(7) may compete energetically (Scheme 4). For this process,
we computed an activation enthalpy of 38.7 kcal mol−1,
whereas the dissociation energy of the S−S bond was 45.0 kcal
mol−1.
In a HVFP experiment performed at 750 °C, almost no
decomposition of 5 was observed. Even if the temperature of
the hot zone was increased to 850 °C, the product mixture in
the argon matrix still contained starting material as the major
component (cf. Figure S1, SI). On the other hand, absorption
bands at 1413.8, 1267.1, 1067.6, 631.3, and 460.1 cm−1
confirmed the presence of 2. In addition, the bands located

Scheme 4. Competing Thermal Decomposition Pathways of S-Methylmethanethiosulfonate (5)

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The Journal of Physical Chemistry A
at 987.4 and 1055.2 cm−1 provided evidence for the formation
of thioformaldehyde (CH2S).30,31 Similarly to the experiment
carried out with 4, the pyrolysate contained substantial
amounts of sulfur dioxide (SO2).
■
CONCLUSION
The present study shows that the methylsulfonyl radical (2) is
kinetically much less stable than the previously reported
methylsulfinyl radical (1). The reason for the observed
differences in the stability of both radicals is the high
dissociation energy of the C−S bond in 1 computed to be
47.5 kcal mol−1. In marked contrast, the BDE of the
corresponding bond in 2 is computed to be only 14.6 kcal
mol−1. Despite these unfavorable energetics, HVFP can be used
to generate 2 using readily available allylmethylsulfone (4) as a
precursor. This method establishes a new convenient approach
for the gas-phase generation of 2 based on a single precursor
molecule.
■
ASSOCIATED CONTENT
*
S Supporting Information
Additional spectroscopic data and computational results
(optimized geometry, energies, Cartesian coordinates, and
vibrational harmonic frequencies of optimized geometries).
This material is available free of charge via the Internet at
http://pubs.acs.org.
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail: Hans.P.Reisenauer@org.chemie.uni-giessen.de. Tele-
phone: (+49)-6419934380 (H.P.R.).
*E-mail: gmloston@uni.lodz.pl (G.M.).
Author Contributions
The ideas were conceived and the experiments planned by all
authors. Measurements and computations were carried out by
H.P.R. All authors wrote the manuscript. All authors have given
approval to the final version of the manuscript.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the DAAD (University Partnership
between the University of Lodz and the Justus-Liebig
University). G.M. acknowledges the National Science Center
(PL-Cracow) for financial support (Grant Maestro−3 (Dec−
2012/06/A/ST5/00219).
■
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