Theoretical Investigation of Carbon–Sulfur Triple Bonds

Denis, Pablo A.; Iribarne, Federico

doi:10.1002/chem.201002840

Cited by 9 publications

(5 citation statements)

References 48 publications

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“…The strongest band at 815.9 cm –1 corresponds to the bending mode (ρ(HCS)) with a 13 C-shift of 4.5 cm –1 . The weaker band at 1178.5 cm –1 is reasonably assigned to the ν(CS) mode due to the large 13 C-shift of 30.8 cm –1 , and the frequency is close to the same mode found in HCSOH (1201.3 cm –1 , Ar-matrix) which contains a formal carbon–sulfur triple bond. − In line with the CS multiple bonds in HCS· and HCSOH, the associated frequencies in both molecules are higher than those in H 2 CS (1055.2 cm –1 ). The ν(CH) mode in HCS· appears at 2989.3 cm –1 with a 13 C-shift of 9.8 cm –1 .…”

supporting

confidence: 53%

Identification and Photochemistry of the Mercaptomethyl Radical

Shao,

Wu,

Wang

et al. 2023

J. Phys. Chem. Lett.

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The mercaptomethyl radical (·CH2SH) is a higher-energy isomer of the methylthio radical (CH3S·) that has been proposed as an important intermediate in atmospheric and interstellar sulfur chemistry. Herein, we report the spectroscopic identification of ·CH2SH during the UV (365 nm) photolysis of CH3S· in a solid Ar-matrix at 10 K. Upon subsequent irradiation at 266 nm, the dehydrogenation of ·CH2SH to yield CS via the intermediacy of the elusive thioformyl radical (HCS·) has also been observed. The characterization of ·CH2SH and HCS· with matrix-isolation IR and UV–vis spectroscopy is supported by 13C-isotope labeling and quantum chemical calculations at the CCSD(T)-F12a/cc-pVTZ-F12 level using configuration-selective vibrational configuration interaction theory (VCI). The disclosed photochemistry of ·CH2SH provides new insight into understanding the chemical evolution of organosulfur molecules in the interstellar medium (ISM).

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confidence: 53%

Identification and Photochemistry of the Mercaptomethyl Radical

Shao,

Wu,

Wang

et al. 2023

J. Phys. Chem. Lett.

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“…8 The number of species prepared based on this principle is constantly increasing. 9 Among others, the relatively stable (phosphanyl)-(trifluoromethyl)carbene was recently characterized spectroscopically and kept for days in solution at −30 °C. 10 At the same time, the methoxytrifluoromethylcarbene (MeO−C(:)− CF 3 ) turned out to be highly unstable.…”

Section: ■ Introductionmentioning

confidence: 99%

“…However, it is known that the quite stable Bertrand-type push–pull carbenes possess rather small Δ E ST magnitudes, ,− which was previously explained by their existing in the phosphaacetylene mesomeric form . The number of species prepared based on this principle is constantly increasing . Among others, the relatively stable (phosphanyl)(trifluoromethyl)carbene was recently characterized spectroscopically and kept for days in solution at −30 °C .…”

Section: Introductionmentioning

confidence: 99%

On the Stability of Perfluoroalkyl-Substituted Singlet Carbenes: A Coupled-Cluster Quantum Chemical Study

2014

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A series of trifluoromethyl-substituted carbenes R-C(:)-CF3 (R = NMe2, OMe, F, PMe2, P(NMe2)2, P(N(Pr-i)2)2, SMe, Cl); (dimethylamino)(perfluoroalkyl)carbenes Me2N-C(:)-R (R = CF3, C2F5, n-C3F7, i-C3F7, and t-C4F9) and symmetrically substituted carbenes R-C(:)-R (R = NMe2, OMe, F, PMe2, SMe, Cl) have been investigated by means of quantum chemistry methods. Different levels of approximation were used, including the CCSD(T) approach also known in quantum chemistry as the "golden standard", in combination with three different basis sets (TZVP, cc-pVDZ, cc-pVTZ). Relative stabilities of carbenes have been estimated using the differences between the singlet and triplet ground state energies (ΔEST) and energies of the hydrogenation reaction for the singlet and triplet ground states of the carbenes. The latter seem to correlate better with stability of carbenes than the ΔEST values. The (13)C NMR chemical shifts of the methylidene carbon indicate the more high-field chemical shift values in the known, isolable carbenes compared to the unstable ones. This is the first report on the expected chemical shifts in the highly unstable singlet carbenes. Using these criteria, some carbene structures from the studied series (as, for instance, Me2N-C(:)-CF3, Me2N-C(:)-C3F7-i) are proposed as good candidates for the experimental preparation.

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“…Denis and Iribarne155 investigated several molecules which were assumed to contain carbon–sulfur triple bonds. The geometries of HOSCH,126 H 3 SCH, and FCSF156 as well as their fragmentation products were optimized at the CCSDT/cc‐pCVQZ level of theory.…”

Section: Computational Characterization Of Carbenesmentioning

confidence: 99%

Computational methods for contemporary carbene chemistry

Gerbig

Ley

2012

WIREs Comput Mol Sci

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The use of computational methods in carbene chemistry has a long-standing tradition. Indeed, the field has come a long way since the first ab initio calculations on methylene. Computations now routinely accompany most experimental studies, either to validate the obtained results or to help design appropriate experiments. Advances in computational carbene chemistry within the last decade are covered in this text, encompassing a plethora of studies on alkyl-, aryl-, halo-, and heterocarbenes (N, P, O, S) as well as on persistent triplet carbenes. Moreover, the conceptual advancements in the fields of theoretical chemistry and computing technology have enabled researchers to conduct intricate ab initio studies. The application of leading-edge theory to multireference problems, high-accuracy thermochemical evaluations, atom tunneling, and the description of bonding is thoroughly reviewed. In addition, general recommendations for the choice of an appropriate method for a specific computational problem are given. Practitioners of the art are likely to discover new computational approaches in carbene chemistry applied to various examples from the current literature. C 2012 John Wiley & Sons, Ltd.

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Theoretical Investigation of Carbon–Sulfur Triple Bonds

Cited by 9 publications

References 48 publications

Identification and Photochemistry of the Mercaptomethyl Radical

Identification and Photochemistry of the Mercaptomethyl Radical

On the Stability of Perfluoroalkyl-Substituted Singlet Carbenes: A Coupled-Cluster Quantum Chemical Study

Computational methods for contemporary carbene chemistry

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