Low-temperature matrix isolation of thiirenes

Torres, M. Rosario; Clement, A.; Bertie, J. E.; Gunning, H. E.; Strausz, O. P.

doi:10.1021/jo00406a045

Cited by 80 publications

(49 citation statements)

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“…[117] FVT causes Wolff rearrangement to thioketene 13. [20,21] The same thioketene is obtained by FVT of benzodithiolone 171, or of benzothiophenedione 11, through benzothiet-2-one (12) (cf.…”

Section: Thioketenes From 123-thiadiazoles and 12-dithiolesmentioning

confidence: 99%

Formation of Cumulenes, Triple-Bonded, and Related Compounds by Flash Vacuum Thermolysis of Five-Membered Heterocycles

Yranzo¹,

Elguero²,

Flammang³

et al. 2001

Eur. J. Org. Chem.

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Section: Thioketenes From 123-thiadiazoles and 12-dithiolesmentioning

confidence: 99%

Formation of Cumulenes, Triple-Bonded, and Related Compounds by Flash Vacuum Thermolysis of Five-Membered Heterocycles

Yranzo¹,

Elguero²,

Flammang³

et al. 2001

Eur. J. Org. Chem.

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“…This The thiirene molecule (1) is another small highly reactive molecule synthesized in a frozen /S\ HC -CH matrix and identified by its IR spectrum (28,29). Although it has only been known a short time, there have already been several changes in its assigned experimental spectrum.…”

Section: Re Sultsmentioning

confidence: 99%

“…Figure 6 shows the four steps in this evolution, with experimental spectra above and the same 4-31G cm-' theoretical spectrum below in each of the sections. Figure 6a is from the original spectrum published by Strausz and coworkers (29). Intensities are given only as strong, medium or weak, and only the coarsest details of the observed spectrum have been assigned.…”

Section: Re Sultsmentioning

confidence: 99%

Theoretical vibrational spectra as a tool in the identification of unusual organic molecules

Heß¹,

Schaad²,

Čárský³

1983

Pure and Applied Chemistry

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-Reactive organic systems are often synthesized at low temperature in a frozen matrix and identified by their IR spectra.Typically these are low resolution spectra contamiflated by reactants and other products. In such cases theoretical vibrational spectra, computed initio, can be of help in the identification and analysis of these spectra.Thus the theoretical IR spectrum of cyclobutadiene is in accord with a rectangular rather than square structure. An experiment that was thought to show the contrary by proving the identity of cyclobutadiene-1,2--d2 and -1,4--d2 is reinterpreted as having obtained an equal mixture of these nonequivalent isomers. Similarly revisions are suggested in the interpretation of the observed spectrum of thiirene. In particular, the C-S bond is calculated to be abnormally long and weak, and the corresponding stretching vibration is predicted at unusually low frequency.

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“…The 4n-.rr electron antiaromatic character of thiirene is manifested by the low C-S bond energy, 14 kcal/mol (14), as compared to that in the saturated counterpart, thiirane, which has a value of >40 kcal/mol (14-16) and explains the ability of thiirene to undergo a facile ring expansion reaction with acetylene to give thiophene Since the late seventies, thiirene and a series of its derivatives, thioketene and ethynylthiol, have been isolated and identified by ir spectroscopy in low temperature inert matrices from the photolysis of 1,2,3,-thiadiazoles (17)(18)(19)(20), where the intervention of thiirene as a novel intermediate had been postulated a decade earlier (3, 5, 6). Recently, the photolysis of trithiocarbonates has been shown to be a superior source of thiirene (19) and the isolation and esr identification of a thioketocarbene, namely, the To state thiobenzoylphenylmethylene, has also been accomplished (21).…”

Section: S('d)+ Hc=ch -Hc=ch-s ( S I ) Ah--46 Kcal/mol [3] S('d) + mentioning

confidence: 99%

Thiirene formation in the reactions of sulfur atoms with alkynes

Verkoczy¹,

Sherwood²,

Safarik³

et al. 1983

Can. J. Chem.

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The gas phase reactions of S(1D2) and S(3PJ) atoms with alkynes have been studied by photolyzing COS in the presence of CH≡CH, CF3C≡CH, and CF3C≡CCF3. In the reactions with CH≡CH, CS2, benzene, and thiophene were formed; with CF3C≡CH, eight products were found with disubstituted thiophenes and trisubstituted benzenes as the major products. In the case of CF3C≡CCF3, only perfluorotetramethylthiophene was detected at low conversion but at long photolysis several new products were observed. Many of the reaction products characterized here have not been reported before.The formation and distribution of the reaction products could be rationalized by an overall mechanism in which the formation of the highly reactive primary adducts, thiirene and thioformylmethylene, is followed by bimolecular reactions yielding the principal end products. The formation of minor products could be explained by secondary photoisomerizations, secondary photolysis, and by secondary decompositions and the secondary reactions of sulfur atoms with primary products.

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Low-temperature matrix isolation of thiirenes

Cited by 80 publications

References 0 publications

Formation of Cumulenes, Triple-Bonded, and Related Compounds by Flash Vacuum Thermolysis of Five-Membered Heterocycles

Formation of Cumulenes, Triple-Bonded, and Related Compounds by Flash Vacuum Thermolysis of Five-Membered Heterocycles

Theoretical vibrational spectra as a tool in the identification of unusual organic molecules

Thiirene formation in the reactions of sulfur atoms with alkynes

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