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Table 1 Computed electronic transitions of 3 from the electronic ground state Notes and references
to the first three lowest excited states (TD-UB3LYP/6-311+G(3df,3pd)) and
1
(a) R. J. Charlson, J. E. Lovelock, M. O. Andreae and S. G. Warren,
Nature, 1987, 326, 655; (b) B. Albrecht, Science, 1989, 245, 1227; (c) R. J.
Charlson, S. E. Schwarz, J. M. Hales, R. D. Cess, J. A. Coakley, Jr.,
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experimental UV/Vis bands of 3 (Ar, 10 K)
State
E (eV)
lmax (nm)
Osc. str.
Trans.
Exptl. lmax (nm)
2
00
00
A, A
2.295
4.853
4.954
540
255
250
0.0005
0.0001
0.0343
n - p*
p - p*
p - p*
ca. 530
n.o.
ca. 260
2
B, A
2
0
C, A
2 (a) G. S. Tyndall and A. R. Ravishankara, Int. J. Chem. Kinet., 1991,
3, 483; (b) S. B. Barone, A. A. Turnipseed and A. R. Ravishankara,
2
Faraday Discuss., 1995, 100, 39; (c) I. Barnes, J. Hjorth and
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(a) S. M. Resende and F. R. Ornellas, Chem. Phys. Lett., 2003, 367, 489;
The knowledge about the position of the absorption bands of 3
allows irradiation at specific wavelengths. While excitation with visible
light did not induce photochemical transformations even after long
irradiation times, photolysis of the matrix with selected wavelengths
corresponding to the more intense UV-band of 3 (248 nm, 254 nm,
and 290 nm) led to the simultaneous disappearance of both the IR as
well as UV/Vis bands of 3. After photolysis a mixture of products such
3
4
(b) X. Li, L. Meng and S. Zheng, THEOCHEM, 2007, 847, 52; (c) X.-Y. Li,
L.-P. Meng and S.-J. Zheng, Chin. J. Chem., 2007, 25, 1480; (d) R. Asatryan
and J. W. Bozzelli, Phys. Chem. Chem. Phys., 2008, 10, 1769; (e) X. Li,
L. Meng, Z. Sun and S. Zheng, THEOCHEM, 2008, 870, 53; ( f ) A. Lesar,
Int. J. Quantum Chem., 2012, 112, 1904; (g) Z. Salta, A. M. Kosmas and
A. Lesar, Comput. Theor. Chem., 2012, 1001, 67.
2
as CO, COS, H O, CS, and thioformic acid was identified based on the
IR absorption bands. Despite this rather unspecific decomposition,
the differences between the spectra taken before and after irradiation
allowed enhancement of the spectral features of 3, as shown in Fig. 1.
Note that upon photolysis the photocylization of 7 leading to the
5 (a) G. K. Buerk and G. Schoffa, Int. J. Protein Res., 1969, 1, 113;
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Norman and H. A. H. Laue, J. Chem. Soc., Perkin Trans. 2, 1977, 497;
(
4
17d
cyclopropyl radical was largely suppressed.
(
f ) D. J. Nelson, J. Phys. Chem., 1978, 82, 1400; (g) S. G. Swarts,
In an extension of this study, we also tested dimethyl
D. Becker, S. DeBolt and M. D. Sevilla, J. Phys. Chem., 1989, 93, 155.
6 F. Turecek, D. E. Drinkwater and F. W. McLafferty, J. Am. Chem. Soc.,
1989, 111, 7696.
sulfoxide (8) as an alternative precursor for thermally generated
ꢀ
3
in the reaction H
3
C(SO)CH
3
- 3 + CH
3
. In accordance with
7
W.-C. Hung, M.-Y. Shen, Y.-P. Lee, N.-S. Wang and B.-M. Cheng,
J. Chem. Phys., 1996, 105, 7402; B.-M. Cheng, E. P. Chew, W.-C. Hung,
J. Eberhard and Y.-P. Lee, J. Synchrotron Radiat., 1998, 5, 1041.
the expected increase of the CS bond dissociation energy as
compared to precursor 4a (computed at B3LYP/6-311+G(3df,3pd):
ꢁ
1
8 L.-K. Chu and Y.-P. Lee, J. Chem. Phys., 2010, 133, 184303.
2
1 kcal mol ), this pyrolysis had to be performed at a signifi-
9
(a) D. A. Blank, S. W. North, D. Stranges, A. G. Suits and Y. P. Lee,
J. Chem. Phys., 1997, 106, 539; (b) G. M. Thorson, C. M. Cheatum,
M. J. Coffey and F. Fleming Crim, J. Chem. Phys., 1999, 110, 10843;
cantly higher temperature (800 1C).
The pyrolysate collected in the Ar matrix was analysed by means
of IR spectroscopy. In this case, however, the characteristic bands
of 3 and those of the methyl radical were observed along with the
unconverted starting material, forming a major component of the
collected pyrolysate. In addition, small amounts of 5, and methane
were also observed. Hence, 8 is a poor precursor of 3.
(
c) J.-W. Ho, W.-K. Chen and P. Y. Cheng, J. Am. Chem. Soc., 2007, 129, 3784.
1
0 (a) H. Gross, Y. He, M. Quack, A. Schmid and G. Seyfang, Chem. Phys.
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1
1
1 D. L. Singleton, R. S. Irwin and R. J. Cvetanovic, Can. J. Chem., 1983,
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13
In summary, radical 3 as well as its D - and C-isotopologues
3
93, 2426; (c) F. Domine, A. R. Ravishankara and C. J. Howard, J. Phys.
were generated by high-vacuum flash pyrolysis and isolated in solid
argon at 10 K starting either with allylmethyl sulfoxide (4a) or its
isotopologues 4b and 4c, respectively, or with dimethyl sulfoxide (8).
The identity of 3 was unambiguously confirmed based on the good
agreement of measured and computed IR spectra at the AE-CCSD(T)/
cc-pVTZ level of theory. The recorded UV/Vis spectrum showing a
very weak band in the visible range (635–450 nm) due to an n - p*
transition and a more intense p - p* absorption (lmax D 260 nm)
corresponds well with TD-DFT computations. As evident from the IR
spectra, photolysis of 3 using UV light (l o 300 nm) leads to an
unspecific decomposition. The presented new method for the
efficient generation of 3 opens the door to further studies on the
structures of products formed in its reactions with atmospheric
Chem., 1992, 96, 2171; (d) A. Kukui, V. Bossoutrot, G. Laverdet and
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1
1
(
c) H. P. Reisenauer, G. Mloston, J. Romanski and P. R. Schreiner, Eur. J.
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G. Mloston, J. Romanski and P. R. Schreiner, Eur. J. Org. Chem., 2012, 3480.
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1
1
5 D. E. Powers, C. A. Arrington, W. C. Harris, E. Block and V. F. Kalasinsky,
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2 2 2
gases such as O , O or NO . These reactions have been postulated
Soc., 2010, 132, 16759.
to be the main degradation pathways for 3 in the atmosphere and 17 (a) G. Maier, H. P. Reisenauer, B. Rohde and K. Dehnicke,
Chem. Ber., 1983, 116, 7323; (b) A. K. Mal’tsev, V. A. Korolov and
O. M. Nefedov, Bull. Acad. Sci. USSR Div. Chem. Sci., 1982, 2131;
they deserve further in-depth investigation.
We dedicate this work to our dear colleague Bogusław Kryczka
(
c) A. K. Mal’tsev, V. A. Korolov and O. M. Nefedov, Bull. Acad. Sci.
on the occasion of his 70th birthday. This work was supported by
the DAAD Partnership of the University of Lodz and the Justus-
Liebig University. G. M. thanks the National Science Center (Poland)
for financial support (Project Maestro-3; Dec-2012/06/A/ST5/00219).
USSR Div. Chem. Sci., 1984, 510; (d) K. Holtzhauer, C. Cometta-
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8 B. Prabhuswamy and S. Y. Ambekar, Synth. Commun., 1999, 29, 3477;
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1
This journal is c The Royal Society of Chemistry 2013
Chem. Commun., 2013, 49, 9467--9469 9469