Microwave Spectrum of 3-Butyne-1-thiol:  Evidence for Intramolecular S−H···π Hydrogen Bonding

Cole, George C.; Møllendal, Harald; Guillemin, Jean‐Claude

doi:10.1021/jp062093y

Cited by 28 publications

(33 citation statements)

References 32 publications

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“…In a recent work [16], we have published the results obtained from a calorimetric and computational study of the thermochemistry of 3-buten-1-ol and 3-butyn-1-ol concluding that the weak intramolecular hydrogen bond from the OH hydrogen to the p-bond charge cloud that exists in both compounds has not significant influence on the enthalpy of formation of these species. Very recently, a similar intramolecular SHÁ Á Áp hydrogen bonding interaction has been reported for a thiol analogue, 3-butyn-1-thiol, in a study of its microwave spectrum [17].…”

Section: Introductionsupporting

confidence: 66%

Experimental and computational thermochemical study of 3-hydroxypropanenitrile

Roux¹,

Notario²,

Vélez³

et al. 2007

The Journal of Chemical Thermodynamics

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Section: Introductionsupporting

confidence: 66%

Experimental and computational thermochemical study of 3-hydroxypropanenitrile

Roux¹,

Notario²,

Vélez³

et al. 2007

The Journal of Chemical Thermodynamics

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“…Another example is 3-mercaptopropionitrile (HSCH 2 CH 2 CtN), 34 in which its most stable conformer seems to be stabilized by this interaction. Another similar example where the thiol group interacts with a triple bond is seen in 3-butyne-1-thiol (HSCH 2 CH 2 CtCH), 35 where a CtC bond is the proton acceptor group.…”

Section: Quantum Chemical Calculations and Microwave Studymentioning

confidence: 97%

Synthesis and Characterization of (E)- and (Z)-3-Mercapto-2-propenenitrile. Microwave Spectrum of the Z-Isomer

et al. 2007

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The kinetically unstable compound 3-mercapto-2-propenenitrile (HS-CH=CH-C[triple bond]N) has been prepared for the first time by flash vacuum pyrolysis at 800 degrees C of 3-(tert-butylthio)-2-propenenitrile with a yield of 77% and a Z:E ratio of 8:1. Several deuterium and 15N isotopologues were also prepared using isotopically enriched compounds. Quantum chemical calculations of the structural and conformational properties of the Z- and E-isomers were undertaken at the B3LYP/6-311++G(3df,2pd), MP2/6-311++G(3df,2pd), MP2/aug-cc-pVTZ, and G3 levels of theory. These methods all predict that the Z- and the E-forms each have two "stable" planar rotameric forms with the H-S-C=C link of atoms in either a synperiplanar or an antiperiplanar conformation, with the synperiplanar form of the Z-isomer as the global minimum. The Z-isomer has been investigated by means of Stark-modulation microwave spectroscopy. Spectra attributable to the parent and three deuterium-substituted isotopologues of a single conformer were recorded and assigned. Additionally, the spectrum belonging to the first excited state of the lowest bending vibration was assigned. The ground-state rotational constants obtained by the least-squares analysis of these transitions were found to be in excellent agreement with the corresponding approximate equilibrium values generated by the MP2/aug-cc-pVTZ calculations. The preferred conformer of this molecule was found to have a synperiplanar arrangement of the H-S-C=C chain of atoms and a planar or nearly planar geometry, with a stabilizing intramolecular hydrogen bond formed between the H atom of the thiol group and pi-electron density associated with the C[triple bond]N triple bond. The possible astrochemical/astrobiological significance of this compound is discussed.

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“…Additionally, the combination of microwave spectroscopy and internally cooled supersonic jets offers the possibility to generate, stabilize and probe weaklybound aggregates and to analyze the interaction forces [5,6,7]. To date, rotationally resolved investigations of thiols and related sulfides have included mostly small alkyl derivatives like ethanethiol [8], ethanedithiol [9], propanethiol [10], propanedithiol [11], 3-butene-1-thiol [12], 3-butyne-1-thiol [13], cyclopropanemethanethiol [14], mercaptoacetonitrile [15], furfuryl mercaptane [7], diethyldisulfide [16], diallyldisulfide [17] and diphenyldisulfide [18]. For selenols, the 2-propene [19], 3-butene [20], 3-butyne [21], cyclopropylmethyl [22] and propargyl [23] derivatives have been studied.…”

Section: The Interest and Characteristics Of Sulfur-centered Hydrogenmentioning

confidence: 99%

Rotational spectrum and intramolecular hydrogen bonding in 1,2-butanedithiol

Juanes

Saragi

Jin

et al. 2020

Journal of Molecular Structure

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The jet-cooled rotational spectrum of 1,2-butanedithiol was observed in the frequency region 2-8 GHz. Two conformers were detected for the molecule, corresponding to trans-and gauchecarbon molecular skeletons, both sharing a gauche arrangement of the two thiol groups. The structural analysis included a ground-state effective structure, isotopic substitution coordinates, B3LYP-D3(BJ) density functional molecular orbital calculations and non-covalent interactions mapping with NCIPlot. The structural data confirm that the two thiol groups synchronize their orientation either parallel or antiparallel to support intramolecular S-H•••S weak hydrogen bonding, reminiscent of the intramolecular hydrogen bond networks observed with adjacent alcohol groups. DFT calculations on 1,2-butanediol and 1,2-ethanedithiol offered structural comparisons with the title compound.

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Microwave Spectrum of 3-Butyne-1-thiol: Evidence for Intramolecular S−H···π Hydrogen Bonding

Cited by 28 publications

References 32 publications

Experimental and computational thermochemical study of 3-hydroxypropanenitrile

Experimental and computational thermochemical study of 3-hydroxypropanenitrile

Synthesis and Characterization of (E)- and (Z)-3-Mercapto-2-propenenitrile. Microwave Spectrum of the Z-Isomer

Rotational spectrum and intramolecular hydrogen bonding in 1,2-butanedithiol

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