Molecular structure of dimethylthiocarbamoyl chloride according to gas phase electron diffraction data andAB INITIO calculations

Naumov, V. A.; Ziatdinova, R. N.; Tafipol'skii, M. A.; Novikov, V. A.

doi:10.1007/bf02742015

Cited by 2 publications

(11 citation statements)

References 2 publications

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“…However, the observed contraction in the r(C(X)-N) bond when comparing the amides (X ) O) 6,7 with the corresponding TFA and TCC thioamides (X ) S) were reproduced at the MP2/ 6-31+G(d,p) level of theory. Also, it was seen from Table 8 that there were some significant differences between the previously reported results for TCC 8 and the results in the present work. The r g (CdS) bond distance was found to be significantly higher in the previous work, 8 having a r g value of 1.652(5) Å compared to 1.641(3) Å observed for TCC in the present work.…”

Section: Discussioncontrasting

confidence: 93%

“…Also, it was seen from Table 8 that there were some significant differences between the previously reported results for TCC 8 and the results in the present work. The r g (CdS) bond distance was found to be significantly higher in the previous work, 8 having a r g value of 1.652(5) Å compared to 1.641(3) Å observed for TCC in the present work. The value from the MP4(SDQ) calculations was 1.649 Å, whereas it was 1.638 Å at the MP2 level, see Table 5.…”

Section: Discussioncontrasting

confidence: 93%

“…The fluoro-substitution increased this value further by about 1.7 kcal mol -1 , which was in accordance with the resonance arguments discussed previously for the presence of a higher electronegative substituent on the carbonyl carbon atom, see Scheme 1. However, in strong contrast to the experimental value of 15.4-(1) kcal mol -1 found for the rotational energy barrier in N,Ndimethylcarbamoyl chloride, the semiempirical PM3 value reported by Naumov et al 8 was less than 4 kcal mol -1 . The corresponding PM3 value calculated for TCC was in better agreement with our calculated MP2 value at about 14 kcal mol -1 .…”

Section: Discussioncontrasting

confidence: 69%

“…7 In this article, we present a continuation of the studies on these interesting compounds with the pair of molecules N,Ndimethylthioformamide (H-C(dS)-N(CH 3 ) 2 , TFA; Figure 1) and N,N-dimethylthiocarbamoyl chloride (Cl-C(dS)-N(CH 3 ) 2 , TCC; Figure 1). Results for the latter molecule were published by Naumov et al 8 after our work was started, and a comparison to their work will be made for TCC. Because we were interested in comparisons of results for TFA and TCC, we felt that the experimental conditions for the two experiments ought to be as similiar as possible.…”

Section: Introductionmentioning

confidence: 83%

“…The corresponding PM3 value calculated for TCC was in better agreement with our calculated MP2 value at about 14 kcal mol -1 . 8 In their work on N,N-dimethylformamide and N,Ndimethylacetamide, 23 Wiberg et al calculated the methyl rotational barriers at the HF/6-31+G(d,p) level. They found values of 0.8 and 1.9 kcal mol -1 for the ground-state barriers of N-Me(syn) and N-Me(anti), respectively, where syn and anti refers to the position of the N-Me bond in relation to the CdO bond.…”

Section: Discussionmentioning

confidence: 99%

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N,N-Dimethylthioformamide and N,N-Dimethylthiocarbamoyl Chloride: Molecular Structure by Gas-Phase Electron Diffraction and ab Initio Molecular Orbital and Density Functional Theory Calculations

Johansen

Hagen

2003

J. Phys. Chem. A

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The molecular structures and the dimethyl rotamer properties of N,N-dimethylthioformamide (TFA) and N,Ndimethylthiocarbamoyl chloride (TCC) have been investigated using gas-phase electron diffraction (GED) data recorded at a temperature of 25 °C, together with ab initio molecular orbital (MO) and density functional theory (DFT) calculations, as well as normal coordinate analysis (NCA) using MP2/6-31+G(d,p) scaled force fields. The molecules exist in the gas phase as a single near-planar conformer, not exhibiting true C s symmetry. The orientation of the two methyl groups on the nitrogen atom have been closely examined by ab initio MO and DFT calculations, and these have been found to be oriented differently in the two molecules. Relevant structural parameter values obtained from the GED refinements, using values from the MP2/6-31+G(d,p) calculations as constraints, were as follows (values under C 1 symmetry assumption with estimated 2σ uncertainties): For TFA, bond lengths (r g ) were r(CdS) ) 1.649(2) Å, r(C 2 -N) ) 1.346(3) Å, r(〈C 5,9 -N〉) ) 1.463( 2) Å (av), r(〈C-H〉) ) 1.125( 4) Å (av), bond angles (∠ R ) were ∠NC 2 S ) 127.0(3)°, ∠〈C 2 NC 5,9 〉 ) 121.8( 5)°(av), ∠〈NC 5,9 H〉 ) 110.4(7)°, and torsion angle φ 1 (S 3 -C 2 -N 1 -C 5 ) ) 12.8°( 2.7°. For TCC, bond lengths (r g ) were r(CdS) ) 1.641(3) Å, r(C 2 -N) ) 1.348(4) Å, r(C 2 -Cl) ) 1.772(4) Å, r(〈C 5,9 -N〉) ) 1.472(3) Å (av), r(〈C-H〉) ) 1.109( 8) Å (av), bond angles (∠ R ) were ∠NC 2 S ) 127.4(6)°, ∠〈C 2 NC 5,9 〉 ) 122.0(6)°(av), ∠〈NC 2 Cl〉 ) 113.0(4)°, and torsion angle φ 1 (S 3 -C 2 -N 1 -C 5 ) ) -5.5°( 10.1°. The results are discussed and compared with the oxygen analogues and previous results for the TCC molecule, as well as with similar molecules in the literature.

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Section: Discussioncontrasting

confidence: 93%

Section: Discussioncontrasting

confidence: 93%

Section: Discussioncontrasting

confidence: 69%

Section: Introductionmentioning

confidence: 83%

Section: Discussionmentioning

confidence: 99%

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