Capture of SO3 isomers in the oxidation of sulfur monoxide with molecular oxygen

Article abstract of DOI:10.1039/c7cc09389f

When mixing SO with O₂ in N₂, Ne, or Ar, an end-on complex OS-OO forms in the gas phase and can subsequently be trapped at cryogenic temperatures (2.8-15.0 K). Upon infrared light irradiation, OS-OO converts to SO₃ and SO₂ + O with the concomitant formation of a rare 1,2,3-dioxathiirane 2-oxide, i.e., cyclic OS(O)O. Unexpectedly, the ring-closure of ¹⁶OS-¹⁸O¹⁸O yields a ca. 2:1 mixture of cyclic ¹⁸OS(¹⁶O)¹⁸O and ¹⁶OS(¹⁸O)¹⁸O. The characterization of OS-OO and OS(O)O with IR and UV/Vis spectroscopy is supported by high-level ab initio computations.

Full text of DOI:10.1039/c7cc09389f

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Feng, J. Xu, Y. Lu, H. Wan, A. K. Eckhardt, P. R. SCHREINER, C. Xie, H. Guo and X. Zeng, Chem. Commun.,
2017, DOI: 10.1039/C7CC09389F.
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DOI: 10.1039/C7CC09389F
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Capture of SO3 Isomers in the Oxidation of Sulfur Monoxide
with Molecular Oxygen
Received 00th January 20xx,
Accepted 00th January 20xx
Zhuang Wu,a Bo Lu,a Ruijuan Feng,a Jian Xu,a Yan Lu,a Huabin Wan,a André K. Eckhardt,b Peter R.
Schreiner,b Changjian Xie,c Hua Guoc and Xiaoqing Zeng*a
DOI: 10.1039/x0xx00000x
www.rsc.org/
of SO, SO2 and SO3 has also been proposed to occur in the
atmosphere of both Io (the innermost moon of Jupiter)7 and
Venus.8 However, models developed from studies on Io’s
volcano Pele suggested that recombination of SO with O2
would not happen in Io’s low-temperature atmosphere,
despite an activation barrier of merely 4.8 kcal mol–1.9
When mixing SO with O2 in N2, Ne, or Ar, an end-on complex OS–
OO forms in the gas phase and can subsequently be trapped at
cryogenic temperatures (2.8–15.0 K). Upon infrared light
irradiation, OS–OO converts to SO3 and SO2
+ O with
concomitant formation of a rare 1,2,3-dioxathiirane 2-oxide, i.e.,
cyclic OS(=O)O. Unexpectedly, the ring-closure of 16OS–18O18O
yields a ca. 2:1 mixture of cyclic 18OS(=16O)18O and 16OS(=18O)18O.
The characterization of OS–OO and OS(=O)O with IR and UV/Vis
spectroscopy is supported by high-level ab initio computations.
Although the reaction of SO with O2 to SO3 appears
simple, a stepwise pathway has been proposed in a recent
theoretical study (Scheme 1).10 The oxidation is suggested to
occur by first forming an end-on complex OSOO (
by ring-closure to 1,2,3-dioxathiirane 2-oxide (cyclic OS(=O)O,
). Singlet cyclic OS(=O)O ( ) should be kinetically stable due
b), followed
c
c
Sulfur is the fourteenth most abundant element in Earth’s
crust and it plays important roles in the chemical functioning
of Earth.1 For example, fully oxidized sulfate has been
identified as the major component in “acid rain” and the
cloud condensation nuclei (CCN), and is thus of vital
importance for the global sulfur cycle.2 In addition to
anthropogenic and biological emissions, eruptions of
volcanoes are an important sulfur source in the atmosphere,
in which the most abundant sulfur gases are SO2 and H2S.3
Subsequent photochemistry of both gases yields sulfur
clusters, sulfur oxides, and eventually various sulfate-
containing aerosols in the atmosphere.4
to large activation barriers for ring-opening to either trans-
OSOO (34 kcal mol–1, UCCSD(T)-F12//B3LYP/aug-cc-pVTZ) or
C3v-SO3 (51 kcal mol–1). Metastable cyclic OS(=O)O (
c) has a
singlet ground state with a rather small singlet-triplet energy
gap (ΔEST = –1 kcal mol–1), hence, its isomerization to SO3 (
d)
might be facilitated by spin state crossing.
O
O
O
O
+O2
O
SO
(a)
S
S
O
S
O
O
O
(cis-b)
(c)
(d)
As the initial oxidation product of sulfur, diatomic sulfur
monoxide (SO) can further be oxidized to SO2 and SO3.5 In the
stratosphere, highly reactive SO can reversibly be
regenerated from UV photolysis (190–220 nm) of SO2 (→ SO
+ O), a reaction believed to be responsible for the sulfur
isotope mass-independent fractionation (S-MIF) in Earth’s
atmosphere.5,6 The photo-induced reversible interconversion
Scheme 1 Proposed pathway for the oxidation of SO.10
As an intriguing intermediate, cyclic OS(=O)O has been
also proposed as the link in the photo-oxidation of SO2 with
O3.11 Despite being unobserved in solid Ar-matrix at 11 K, its
involvement in the reaction was rationalized by the
observation of the unexpected 18O-isotopic effects (Scheme
2). Moreover, it was suggested that quantum mechanical
tunneling (QMT) should be responsible for its absence in the
a.College of Chemistry, Chemical Engineering and Materials Science,
Soochow University, Suzhou 215123 China. E-mail: xqzeng@suda.edu.cn
b.Institute of Organic Chemistry, Justus-Liebig University, Heinrich-Buff-Ring
17, 35392 Giessen, Germany
cryogenic matrix due to fast ring-opening to SO3 (route A).
c. Department of Chemistry and Chemical Biology, University of New
Mexico,Albuquerque, NM 87131, USA
†Electronic Supplementary Information (ESI) available: Experimental and
calculation details, IR spectra, calculated data and other electronic format See
DOI: 10.1039/x0xx00000x.
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18O
S
18O
S
1.2
1.0
0.8
0.6
18O
18O
View Article Online
g
A
B
18
O
g
i
i
DOI: 10.1039/C7CC09389F
g
+
18O
+
O
d
S
S
j
j
+18O3
266 nm
D)
C)
i
O
O
O
O
18
O
18
SO2
O
O
d
b
b
d
O
O
OS18O + 18OS18
O
b
S
S
18
g
d
c
O
g
O
c
g
g
c
c
c
i
b
b
Scheme 2 Proposed pathway for the oxidation of SO2.11
b
A
f
g
f
f
0.4
0.2
0.0
b
e
b
e
g
d
*
k
B)
A)
e
f
Experimentally, dioxathiiranes including cyclic SO2 remain
unreported, although this class of species has been
frequently proposed as intermediates in the oxidation of
sulfides.12 Attempts to generate cyclic SO2 through laser (193
nm) photolysis of sulfur dioxide in a solid Ar-matrix at 13 K
led to the formation of SOO.13 The same laser photolysis of
SO3 in an Ar-matrix at 12 K furnishes SO2 and an O atom,
followed by recombination to cis-OSOO, which was identified
by IR spectroscopy.14 Continuing our interest in reactive
sulfur and oxygen intermediates (e.g., CH3SO3,15 OSN,16
HNSO2,17 and CF3SO/CF3OS18), herein, we now report the first
time gas-phase generation of cis-OSOO and the observation
of its photoisomerization to a rare dioxathiirane cyclic
OS(=O)O.
a
h
e
e
e
1800
1600
1400
1200
1000
800
600
 / cm1
Fig.1 A) IR spectrum of matrix isolated HVFP (1000 K)
products of ethylene episulfoxide ( ) in N2 (1:1000) at 15 K. B)
IR spectrum of matrix isolated HVFP (1000 K) products of a
mixture of /O2/N2 (1:50:1000) at 15 K. C) IR difference
spectrum showing the change of the matrix upon 830 nm LED
irradiation (20 min). D) IR difference spectrum showing the
change of the HVFP (1000 K) products of a mixture of
(1:50:1000) upon 365 nm UV-light irradiation (1 min). IR
bands of SO ( ), cis-OSOO ( ), cyclic OS(=O)O ( ), SO3 ),
CH2CH2 ( ), SO2 ( ), OSSO ( ), O3 ( ), CH3C(O)H ( ), CO2 ( ), and
H2O (*) are marked.
e
e
e/O2/N2
a
b
c
(d
f
g
h
i
j
k
As an important building block in synthetic organic sulfur
chemistry, SO can readily be generated through pyrolysis of
episulfoxides.19 A typical IR spectrum of the matrix-isolated
high vacuum flash pyrolysis (HVFP) products of ethylene
range of 600–850 nm, we found that the 830 nm light-
emitting diode (LED) is most effective in depleting OSOO. The
corresponding IR difference spectrum (Fig. 1C) reveals the
complete depletion of cis-OSOO (
formation of SO3 ( ), SO2 ( ), O3 (
, 1041.9 and 704.3 cm–1),23
and a new species ( ) with IR bands at 1299.8, 927.3, 660.9,
629.7, and 459.9 cm–1. When the irradiation changes to UV
light (365 or 266 nm), consumption of OSOO also happens
(Fig. 1D), after which SO2 and SO3 form.
For the spectral assignments, we computed the IR
spectrum of the most likely candidate species cyclic OS(=O)O
episulfoxide (
decomposition of
SO (
, 1139.3 cm–1)20 and ethylene (
1438.4, 947.6, and 829.7 cm–1).21 Additionally, a species with
a prominent IR band at 1103.1 cm–1
) also forms, which is
e
) at ca. 1000 K is shown in Fig. 1A. The
(ca. 80%) is evident from the formation of
, 3106.6, 3076.8, 2989.4,
b) within 20 minutes and
e
d
g
i
a
f
c
(h
tentatively assigned to the SO dimer OSSO based on
comparison with the computed strongest IR band at 1120
cm–1 at the fc-CCSD(T)/cc-pV(Q+d)Z level.22
When performing the HVFP of the episulfoxide (e) in the
(c, Table 1). The good agreement of the observed IR spectrum
presence of O2
spectrum of the matrix-isolated pyrolysate (Fig. 1B) suggests
the disappearance of SO ( ) and OSSO ( ) but the formation
of SO2 ( , 1396.9
(e/O2/N2= 1:50:1000), the resulting IR
with the computational results, particularly with the
anharmonic CCSD(T)/cc-pVTZ IR frequencies, supports the
assignment. The strongest IR band at 1299.8 cm–1 belongs to
the S=O stretching vibration with an isotopic shift of 13.0 cm–
1 (13.8 cm–1, calc.) for the naturally abundant 34S. The band at
927.3 cm–1 is assigned to the O–O stretching vibration that
mixes with the symmetric O–S–O stretch as evident from a
34S-isotopic shift of 5.2 cm–1 (5.0 cm–1, calc.). The asymmetric
O–S–O stretch appears at 629.7 cm–1, and the corresponding
deformation mode locates at 660.9 cm–1 with a 34S-isotopic
shift of 6.4 cm–1 (6.8 cm–1, calc.). Note that traces of cyclic
a
h
g
, 1347.5, 1153.1, and 522.9 cm–1) and SO3 (
d
cm–1).15 In addition, a new species with strong IR bands at
1235.8, 1037.4, and 605.3 cm–1 appears, its assignment to cis-
OSOO (b) is assured by the good agreement with the
previously reported IR frequencies of 1229.6, 1041.3, and
597.6 cm–1 found in an Ar-matrix.14 Due to weak interactions
with surrounding molecules, the band positions observed in
different solid matrices are slightly shifted (Ar-matrix: 1231.2,
1044.6, and 597.9 cm–1; Ne-matrix: 1233.4, 1043.3, and 601.5
cm–1). Therefore, it is clear that the initially generated SO
quantitatively reacted with O2 in the gas phase. The presence
of SO2 and SO3 among the products indicates fragmentation
and isomerization of OSOO under the pyrolysis conditions.
Given the theoretically predicted very weak vertical
transition at 699 nm (oscillator strength f = 0.0001, TD-
B3LYP/6-311+G(3df)) for OSOO, the matrix was first
irradiated with various light sources with wavelengths in the
OS(=O)O (c) can also be identified among the HVFP products
of the /O2/N2 mixture, indicating the occurrence of a
e
thermal conversion from OSOO.
To further verify the assignment and probe the
mechanism for the conversion of various sulfur oxides (SO,
SO2, OSOO, cyclic OS(=O)O, and SO3), isotopic labeling
experiments using 18O2 (97 atom %) for the oxidation of SO
were performed. As expected, OS–18O18O (
b', Fig. 2A) forms
via combination of SO with 18O2. The concomitant generation
2 | Chem. Commun., 2017, 00, 1-3
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of singly 18O-labeled SO2 and traces of doubly 18O-labeled SO3
clearly demonstrates unimolecular dissociation and
isomerization of OS-18O18O in the gas phase.
0.8
0.6
0.4
View Article Online
d'
d'
g'
g"
c"
c'
DOI: 10.1039/C7CC09389F
d'
Unexpectedly, subsequent 830 nm LED irradiation (Fig. 2A)
d'
leads to the formation of a mixture of16OS(=18O)18O (
c
')
"). Given the almost equal intensities for
each IR band computed at the CCSD(T)/cc-pVTZ level for
and " (see the details in the ESI†), a ratio of 2:1 for the two
i"
c"
c'
d'
c"
c'
g'
g"
c"
c'
and18OS(=16O)18O (
c
i'
i"
A)
B)
c
'
d
A
c
d
0.2
b'
isotopomers can be estimated. In sharp contrast to the sole
observation of singly 18O-labeled SO2 during the gas-phase
oxidation of SO with 18O2, a mixture of isotopologues 16OS18O
g
b'
b
b'
d
c
c
g
c
g
i
j
c
c
i
0.0
(g g") is observed among the photolysis
') and 18OS18O (
b
b
products of OS-18O18O with an estimated ratio of about 4:1
based on the intensities of the two well-resolved IR bands at
1124.2 and 1101.5 cm–1, respectively. The mixture of
1800
1600
1400
1200
1000
800
600
 / cm1
16O18O18O ( ') and 18O18O18O (
i i") in a ratio of 1:4 ensues (Fig.
Fig.2 A) IR difference spectrum showing the change of the N2-
matrix isolated HVFP (1000 K) products of a mixture of
2A), which means that the photodissociation (830 nm) of
O=S–OO to OSO and O (immediately trapped by O2 in 5% O2-
doped matrices) occurs likely through the formal cleavage of
either the terminal O–O bond or the O=S bond. The absence
of the SOO intermediate12 in the latter case is probably due
to isomerization to OSO under the irradiation conditions.
e
/18O2/N2 (1:50:1000) upon 830nm LED irradiation (20 min).
For comparison, the corresponding IR difference spectrum
with 16O2 is shown as Fig.2B.The bands of 16OS-18O18O (
'),
16OS(=18O)18O ( '), 18OS(=16O)18O ( "), doubly 18O-labeled SO3
'), 16OS18O ( '), and 18OS18O ( "), 16O18O18O (
'), and
18O18O18O (
") are marked.
b
c
g
c
(d
g
i
i
Nevertheless, only the doubly 18O-labeled SO3
(d') was
obtained as the final oxidation product in the reaction of SO
with 18O2. The abnormal 18O isotopic distributions in the ring-
closure of OS–OO (b) to cyclic OS(=O)O (c) and subsequent
dissociation to SO2 and O suggest that the mechanism might
be more complex than the previously proposed (Scheme 1).
The oxidation of SO and subsequent photochemistry can be
followed by UV/Vis spectroscopy at 12 K (Fig. 3). Consistent
with the observation of an intense red color for the matrix-
predicted very strong vertical transition at 349 nm (f = 0.0962,
TD-B3LYP/6-311+G(3df)) for OSOO. In line with the IR
spectroscopic observation, irradiation of the matrix with 850
nm LED causes depletion of this and another band at 230 nm.
As a result, a band at 255 nm appears but subsequently
vanishes completely upon low-pressure mercury lamp
irradiation (254 nm). By referring to a computed transition at
isolated HVFP products of the
e/O2/N2 mixture, a strong and
290 nm (f = 0.0015), it is assigned to the cyclic OS(=O)O (c). A
structured broad absorption band centered at 410 nm (λmax
)
weak band at 280 nm becomes apparent after 254 nm
irradiation, which is likely associated with the remaining
species in the matrix such as O3, SO3, and the undecomposed
ethylene episulfoxide.
is observed. It is very close to the most characteristic
absorptions found for zwitterionic carbonyl oxides R2C=O+–O–
ranging from300 to 500 nm.24 This is also consistent with a
Table 1. Computed and observed IR spectra (cm–1) of cyclic OS(=O)O (
c).
assignmentg
IR fundamentals
18O isotopic shiftsd
CCSD(T)-F12a
CCSD(T)/cc-pVTZb
Observedc
Ar-matrix
16OS(=18O)18O 18OS(=16O)18O
calc.e obs.f calc.e obs.f
anharmonic
harmonic anharmonic
N2-matrix
1299.8
Ne-matrix
1294.8
1311.7 (243)
940.1 (72)
1308.5
947.1
1291.9 (138) 1296.6
47.1
21.9
43.8
21.6
0.5
0.5
A',
A',


(SO')
(OO)
925.3 (38)
658.1 (40)
618.4 (18)
444.9 (17)
923.9 (52) 927.3 (34) 925.2 (49)
659.5 (27) 660.9 (30) 659.3 (35)
624.3 (16) 629.7 (21) 626.5 (22)
460.0 (35) 459.9 (40) n.o.h
42.1
42.5
669.9 (62)
635.3 (14)
459.1 (27)
672.8
630.9
449.7
13.1
14.7
16.0
11.6
12.7
14.3
24.9
27.4
8.6
24.0
26.9
A',
A",
A',
A",
(OSO)
(O'SO)
344.9 (8)
342.0 (5) 337.6 (5)
10.9
(O'SO)
a
b
c
With the VTZ-F12 basis set. Computed IR intensities (km mol–1) in parentheses. Band positions for the most intense matrix
sites. d 18O-isotopic shifts relative to the IR bands of 16OS(=16O)16O. At the CCSD(T)/cc-pVTZ level. Observed in N2-matrix.
Tentative assignment based on the computed vibrational displacement vectors. h Not observed.
e
f
g
This journal is © The Royal Society of Chemistry 20xx
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365 nm, 5 min
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/O2/N2 (1:50:1000) at 12 K.
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In summary, two SO3 isomers cis-OSOO and dioxathiirane
cyclic OS(=O)O have been identified in the oxidation reaction
of SO with O2 by matrix-isolation IR and UV/Vis spectroscopy.
This dioxathiirane is the first experimentally reported cyclic
SO3 isomer. A stepwise reaction process of OS + O2→ OSOO
→ cyclic OS(=O)O → SO3 has been experimentally unraveled.
The unexpected 18O isotopic distributions observed in the
photo-induced ring-closure of OSOO to cyclic OS(=O)O and
the dissociation of OSOO to SO2 and O requires further
experimental and theoretical studies. The facile generation of
OSOO and cyclic OS(=O)O in the gas phase will stimulate
further studies on their structures and reactivities.
This research was supported by the National Natural
Science Foundation of China (21422304 and 21673147 to
X.Q.Z.), and the Priority Academic Program Development of
Jiangsu Higher Education Institutions (PAPD). Partial support
from the U.S. Department of Energy (DE-SC0015997 to H.G.)
is also acknowledged. A.K.E. was supported through a
fellowship of the Fonds der Chemischen Industrie.
,
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Conflicts of interest
There are no conflicts to declare.
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