The rotational gas-phase spectrum of trans- and cis-HSSOH at 100GHz

Koerber, Monika; Baum, Oliver; Hahn, Ursula; Gauß, Jürgen; Giesen, Thomas

doi:10.1016/j.jms.2009.06.007

Cited by 11 publications

(6 citation statements)

References 38 publications

(38 reference statements)

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“…The formation mechanism of HSOH via decomposition of t -Bu 2 SO was also analyzed quantum chemically to support the experimental findings. The pyrolysis products of t -BuS(O)S t -Bu were analyzed by several groups using IR spectroscopy, rotational spectroscopy, and several high-level theoretical methods. − However, there is no systematic theoretical or experimental analysis for the reaction mechanism and reaction kinetics for the total pyrolysis reaction of t -BuS(O)S t -Bu.…”

Section: Introductionmentioning

confidence: 99%

Pyrolysis of tert-Butyl tert-Butanethiosulfinate, t-BuS(O)St-Bu: A Computational Perspective of the Decomposition Pathways

2011

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A systematic theoretical study has been performed on the low pressure thermal decomposition pathways of t-BuS(O)St-Bu using the CCSD(T)/cc-pV(D+d)Z//B3LYP/6-311++G(2d,2p), CCSD(T)/cc-pV(D+d)Z//PBEPBE/6-311++G(2d,2p), and G3B3 level of theories. Rate constants for the unimolecular decomposition pathways are calculated using Rice−Ramsperger−Kassel−Marcus (RRKM) theory. On the basis of the experimental observation and theoretical predictions, the pyrolysis channels are considered as primary and secondary pyrolysis reactions. The primary decomposition via a five-membered transition state leads to the formation of tert-butanethiosulfoxylic acid (t-BuSSOH) and 2-methylpropene (C4H8) almost exclusively having low-pressure limit rate constant k(1)(0) = 4.67 × 10(−6)T(−4.67) exp(−11.64 kcal mol(−1)/RT) cm3 mol(−1) s(−1) (T = 500−800 K). The primary decomposition via a six-membered transition state is also identified, and that leads to the tert-butanethiosulfinic acid t-BuS(OH)S, which is the branched chain isomer of t-BuSSOH. The formation of t-BuSSOH is thermodynamically as well as kinetically favorable over t-BuS(OH)S formation, and therefore the second product could not be found experimentally. Furthermore, calculation on secondary pyrolysis pathways involving the decomposition of t-BuSSOH leads to the formation of 1-oxatrisulfane (trans-HSSOH and cis-HSSOH) and their branched isomer S(SH)OH. These three secondary product formation rates are competitive, but thermodynamics do not favor the formation of the branched isomer. Among the secondary pyrolysis products, trans-HSSOH is the most stable one, and its formation rate constant at low pressure is calculated to be k(3)(0) = 5.49 × 10(28)T(−10.70) exp(−36.22 kcal mol(−1)/RT) cm3 mol(−1) s(−1) (T = 800−1500 K). Finally, the secondary pyrolysis pathway from less stable product t-BuS(OH)S is also predicted, and that leads to trans-HSSOH and cis-HSSOH products with almost equal rates. A bond-order analysis using Wiberg bond indexes obtained by natural bond orbital (NBO) calculation predicts that the primary and secondary pyrolysis of t-BuS(O)St-Bu occur via E1-like mechanism.

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Section: Introductionmentioning

confidence: 99%

Pyrolysis of tert-Butyl tert-Butanethiosulfinate, t-BuS(O)St-Bu: A Computational Perspective of the Decomposition Pathways

2011

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“…Moreover, sulfoxylic acid is isoelectronic with H 2 S 3 (HSSSH vs HOSOH) and if formed may be liberated into the gas phase. The rotational spectra of HSSSH and the structurally similar HSSOH , have also been measured, and detection of any of these species would provide strong support for the validity of the aforementioned chemical model.…”

Section: Resultsmentioning

confidence: 86%

Microwave Detection of Sulfoxylic Acid (HOSOH)

et al. 2013

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Sulfoxylic acid (HOSOH), a chemical intermediate roughly midway along the path between highly reduced (H2S) and highly oxidized sulfur (H2SO4), has been detected using Fourier transform microwave spectroscopy and double resonance techniques, guided by new high-level CCSD(T) quantum-chemical calculations of its molecular structure. Rotational spectra of the two most stable isomers of HOSOH, the putative ground state with C2 symmetry and the low-lying C(s) rotamer, have been measured to high precision up to 71 GHz, allowing accurate spectroscopic parameters to be derived for both isomers. HOSOH may play a role in atmospheric and interstellar chemistry, and the present work provides the essential data to enable remote sensing and/or radioastronomical searches for these species. Spectroscopic characterization of HOSOH suggests that other transient intermediates in the oxidation of SO2 to H2SO4 may be amenable to laboratory detection as well.

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“…Its existence was also postulated as an intermediate that undergoes further conversion in the gas phase yielding 1‐oxatrisulfane ( 13 ). The structure of 13 was elucidated by analysis of its rotational spectrum as well as that of its isotopologues 4b,4c. Recently, the mechanism of thermolysis of 12 , leading to 13 and S 2 O ( 14 ), was studied by means of computational methods 9.…”

Section: Resultsmentioning

confidence: 99%

Thermolysis of 3,3,5,5‐Tetramethyl‐1,2,4‐trithiolane 1‐Oxide: First Matrix Isolation of the HOSS^· Radical

et al. 2012

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Flash vacuum pyrolysis of 3,3,5,5‐tetramethyl‐1,2,4‐trithiolane 1‐oxide performed at 700 °C yields the 1‐oxatrisulfan‐3‐yl radical (HOSS·) along with disulfur monoxide (S2O) and diisopropyl sulfide, which were isolated in argon matrices at 10 K. Upon irradiation with UV light, the 1‐oxatrisulfan‐3‐yl radical undergoes isomerization to the 1‐oxatrisulfan‐1‐yl radical (HSSO·). Both radicals were identified by comparison of their computed and experimental IR and UV/Vis spectra. In addition, density functional theory (DFT) computations offer a plausible explanation of the most likely reaction mechanism, suggesting that the initial step is a 1,3‐H shift with simultaneous ring opening. A 1‐oxatrisulfane derivative formed thereby undergoes fragmentations via a radical and a competitive concerted pathway leading to the observed final products. The same mechanism also governs the thermal fragmentation of di‐tert‐butyl disulfide S‐oxide. Its pyrolysis at 700 °C affords an analogous set of products, including the 1‐oxatrisulfan‐3‐yl radical (HOSS·) as the key intermediate.

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The rotational gas-phase spectrum of trans- and cis-HSSOH at 100GHz

Cited by 11 publications

References 38 publications

Pyrolysis of tert-Butyl tert-Butanethiosulfinate, t-BuS(O)St-Bu: A Computational Perspective of the Decomposition Pathways

Pyrolysis of tert-Butyl tert-Butanethiosulfinate, t-BuS(O)St-Bu: A Computational Perspective of the Decomposition Pathways

Microwave Detection of Sulfoxylic Acid (HOSOH)

Thermolysis of 3,3,5,5‐Tetramethyl‐1,2,4‐trithiolane 1‐Oxide: First Matrix Isolation of the HOSS^· Radical

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The rotational gas-phase spectrum of trans- and cis-HSSOH at 100GHz

Cited by 11 publications

References 38 publications

Pyrolysis of tert-Butyl tert-Butanethiosulfinate, t-BuS(O)St-Bu: A Computational Perspective of the Decomposition Pathways

Pyrolysis of tert-Butyl tert-Butanethiosulfinate, t-BuS(O)St-Bu: A Computational Perspective of the Decomposition Pathways

Microwave Detection of Sulfoxylic Acid (HOSOH)

Thermolysis of 3,3,5,5‐Tetramethyl‐1,2,4‐trithiolane 1‐Oxide: First Matrix Isolation of the HOSS· Radical

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Thermolysis of 3,3,5,5‐Tetramethyl‐1,2,4‐trithiolane 1‐Oxide: First Matrix Isolation of the HOSS^· Radical