Vibrational spectra andab initio calculations on trichloromethanesulphenyl cyanide, CCl3SCN

Ulic, Sonia E.; Napoli, F.; Hermann, Angelika; Mack, Hans‐Georg; Védova, Carlos O. Della

doi:10.1002/1097-4555(200010)31:10<909::aid-jrs616>3.0.co;2-k

Cited by 6 publications

(6 citation statements)

References 15 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The ν(CCl 3 ) stretching modes are observed in the infrared spectrum at 813, 766, and 738 cm −1 corresponding to ν s (CCl 3 ), ν as (CCl 3 ), and ν as (CCl 3 ), respectively, and this assignment agrees with reported values for similar molecules containing the CCl 3 group. , …”

Section: Resultssupporting

confidence: 89%

“…The ν(CCl 3 ) stretching modes are observed in the infrared spectrum at 813, 766, and 738 cm -1 corresponding to ν s (CCl 3 ), ν as (CCl 3 ), and ν as (CCl 3 ), respectively, and this assignment agrees with reported values for similar molecules containing the CCl 3 group. 26,27 The S-O vibration, the characteristic feature of sulfenic esters, is observed at 757 cm -1 as a weak band in the Raman spectrum of the liquid, and it was assigned by comparison with CF 3 SOC(O)CH 3 28 (762 cm -1 ) and CF 3 SOC(O)CF 3 28 (765 cm -1 ). This mode could not be identified in the IR spectra because of its low intensity and the overlapping with the absorptions of the CCl 3 group.…”

Section: (<1) τ(C-s)/τ(s-o)/τ(o-c)mentioning

confidence: 99%

See 1 more Smart Citation

Synthesis, Spectroscopic Characterization, and Conformational Properties of Trichloromethanesulfenyl Acetate, CCl₃SOC(O)CH₃

Reina

Boese

et al. 2008

J. Phys. Chem. A

View full text Add to dashboard Cite

Trichloromethanesulfenyl acetate, CCl 3SOC(O)CH 3, belongs to the family of sulfenic esters. This molecule has been characterized by vibrational spectroscopy. The conformational and geometrical properties of this species have been determined by IR and Raman spectroscopy, X-ray diffraction, and quantum chemical calculations. Geometry optimizations of the most stable forms were performed with ab initio (HF, MP2) and density functional theory (B3LYP) methods. According to our data, this compound results in a gauche-syn conformer with C 1 symmetry (gauche orientation around the S-O bond and syn orientation of the CO double bond with respect to the S-O single bond) for the most stable geometry, and trans-syn conformer with C s symmetry (trans orientation around the S-O bond and syn orientation of the CO double bond with respect to the S-O single bond) for the second stable conformer (1.1 and 0.53 kcal/mol higher in energy than the most stable C 1 form according to the matrix FTIR spectroscopy and MP2/6-31G* level of the theory, respectively). The crystalline solid (monoclinic, P2 1/ n, a = 8.0152(17) A, b = 5.7922(13) A, c = 17.429(4) A, alpha = gamma = 90 degrees , beta = 100.341(3) degrees ) consists exclusively of the main form. The geometrical parameters (X-ray diffraction) are d C-Cl = 1.767(19) A, d C-S = 1.797(2) A, d S-O = 1.663(14) A, d CO = 1.189(2) A, d O-C = 1.389(3) A, d C-C = 1.483(3) A, angles Cl-C-Cl = 110.3(11) degrees , Cl-C-S = 111.8(12) degrees , C-S-O = 97.4(8) degrees , S-O-C = 116.7(11) degrees , O-CO = 122.8(19) degrees , OC-C = 127.1(2) degrees , and the main torsion angles are delta(CSOC) = 105.9(15) degrees and delta(SOC(O)) = 7.6(3) degrees . The geometrical data calculated with B3LYP/6-31G++(3df,3pd), B3LYP/6-311G++(3df,3pd), B3LYP/aug-cc-pVTZ, and MP2/6-31G* are in good agreement with diffraction data.

show abstract

Section: Resultssupporting

confidence: 89%

Section: (<1) τ(C-s)/τ(s-o)/τ(o-c)mentioning

confidence: 99%

Synthesis, Spectroscopic Characterization, and Conformational Properties of Trichloromethanesulfenyl Acetate, CCl₃SOC(O)CH₃

Reina

Boese

et al. 2008

J. Phys. Chem. A

View full text Add to dashboard Cite

show abstract

“…There is good agreement, as regards both wavenumbers and relative intensities, between the observed and calculated vibrational spectra for the syn form. The bands in the observed spectra have then been assigned on the basis of comparisons (i) with the calculated IR spectrum and (ii) with the spectra of related molecules, most notably ClC(O)OCF 3 and FC(O)OCF 3 , but also taking account of species such as ClC(O)OSO 2 CF 3 11 and CCl 3 SCN are based on the displacement vectors for the relevant fundamentals derived from the B3LYP calculations.…”

Section: Resultsmentioning

confidence: 99%

Trichloromethyl Chloroformate (“Diphosgene”), ClC(O)OCCl₃: Structure and Conformational Properties in the Gaseous and Condensed Phases

et al. 2006

View full text Add to dashboard Cite

The conformational properties of gaseous trichloromethyl chloroformate (or "diphosgene"), ClC(O)OCCl3, have been studied by vibrational spectroscopy [IR (gas), IR (matrix), and Raman (liquid)] and quantum chemical calculations (MP2 and B3LYP with 6-311G basis sets); in addition, the structure of a single crystal at low temperature has been determined by X-ray diffraction. ClC(O)OCCl3 exhibits only one conformational form having Cs symmetry with a synperiplanar orientation of the C-O single bond relative to the C=O double bond. The calculated energy difference between the syn and anti forms, 5.73 kcal mol(-1) (B3LYP) or 7.06 kcal mol(-1) (MP2), is consistent with the experimental findings for the gas and liquid phases. The crystalline solid at 150 K [monoclinic, P2(1)/n, a = 5.5578(5) angstroms, b = 14.2895(12) angstroms, c = 8.6246(7) angstroms, beta = 102.443(2) degrees, Z = 4] likewise consists only of molecules in the syn form.

show abstract

“…Taking into account the singular importance of these kinds of molecules, few spectroscopic data have been reported. The infrared and Raman spectra of both CCl 3 SCN and CCl 2 FSCN molecules have been interpreted in terms of C s and C 1 molecular symmetry, respectively. , Recently, the title molecules have been structurally studied in both gas and crystal phases by means of gas electron diffraction (GED) and low-temperature single-crystal X-ray diffraction (XRD). , The experimental results concluded that the crystal structure of CCl 2 FSCN contains solely the gauche -conformer (FC–SC dihedral angle near to 60°) while in the gas phase both gauche - and anti -conformations (FC–SC dihedral angle near to 180°) are present in equilibrium at room temperature, with the gauche -conformer being the most stable form. On the other hand, the crystal and gas phase conformations of the CCl 3 SCN molecule show that the CCl 3 group results staggered with respect to the SCN group.…”

Section: Introductionmentioning

confidence: 99%

Electronic Properties and Dissociative Photoionization of Thiocyanates, Part III. The Effect of the Group’s Electronegativity in the Valence and Shallow-Core (Sulfur and Chlorine 2p) Regions of CCl₃SCN and CCl₂FSCN

et al. 2017

View full text Add to dashboard Cite

Both photoelectron spectroscopy (PES) data and PhotoElectron-PhotoIon-Coincidence (PEPICO) spectra obtained from a synchrotron facility have been used to examine the electronic structure and the dissociative ionization of halomethyl thiocyantes in the valence and shallow-core S 2p and Cl 2p regions. Two simple and closely related molecules, namely, CClSCN and CClFSCN, have been analyzed to assess the role of halogen substitution in the electronic properties of thiocyanates. The assignment of the He(I) photoelectron spectra has been achieved with the help of quantum chemical calculations at the outer-valence Green's function (OVGF) level of approximation. The first ionization energies observed at 10.55 and 10.78 eV for CClSCN and CClFSCN, respectively, are assigned to ionization processes from the sulfur lone pair orbital [n(S)]. When these molecules are compared with CXSCN (X = H, Cl, F) species, a linear relationship between the vertical first ionization energy and electronegativity of CX group is observed. Irradiation of CClSCN and CClFSCN with photons in the valence energy regions leads to the formation of CClX and CClXSCN ions (X = Cl or F). Additionally, the achievement of the fragmentation patterns and the total ion yield spectra obtained from the PEPICO data in the S 2p and Cl 2p regions and several dissociation channels can be inferred for the core-excited species by using the triple coincidence PEPIPICO (PhotoElectron-PhotoIon-PhotoIon-Coincidence) spectra.

show abstract

Vibrational spectra andab initio calculations on trichloromethanesulphenyl cyanide, CCl3SCN

Cited by 6 publications

References 15 publications

Synthesis, Spectroscopic Characterization, and Conformational Properties of Trichloromethanesulfenyl Acetate, CCl₃SOC(O)CH₃

Synthesis, Spectroscopic Characterization, and Conformational Properties of Trichloromethanesulfenyl Acetate, CCl₃SOC(O)CH₃

Trichloromethyl Chloroformate (“Diphosgene”), ClC(O)OCCl₃: Structure and Conformational Properties in the Gaseous and Condensed Phases

Electronic Properties and Dissociative Photoionization of Thiocyanates, Part III. The Effect of the Group’s Electronegativity in the Valence and Shallow-Core (Sulfur and Chlorine 2p) Regions of CCl₃SCN and CCl₂FSCN

Contact Info

Product

Resources

About

Vibrational spectra andab initio calculations on trichloromethanesulphenyl cyanide, CCl3SCN

Cited by 6 publications

References 15 publications

Synthesis, Spectroscopic Characterization, and Conformational Properties of Trichloromethanesulfenyl Acetate, CCl3SOC(O)CH3

Synthesis, Spectroscopic Characterization, and Conformational Properties of Trichloromethanesulfenyl Acetate, CCl3SOC(O)CH3

Trichloromethyl Chloroformate (“Diphosgene”), ClC(O)OCCl3: Structure and Conformational Properties in the Gaseous and Condensed Phases

Electronic Properties and Dissociative Photoionization of Thiocyanates, Part III. The Effect of the Group’s Electronegativity in the Valence and Shallow-Core (Sulfur and Chlorine 2p) Regions of CCl3SCN and CCl2FSCN

Contact Info

Product

Resources

About

Synthesis, Spectroscopic Characterization, and Conformational Properties of Trichloromethanesulfenyl Acetate, CCl₃SOC(O)CH₃

Synthesis, Spectroscopic Characterization, and Conformational Properties of Trichloromethanesulfenyl Acetate, CCl₃SOC(O)CH₃

Trichloromethyl Chloroformate (“Diphosgene”), ClC(O)OCCl₃: Structure and Conformational Properties in the Gaseous and Condensed Phases

Electronic Properties and Dissociative Photoionization of Thiocyanates, Part III. The Effect of the Group’s Electronegativity in the Valence and Shallow-Core (Sulfur and Chlorine 2p) Regions of CCl₃SCN and CCl₂FSCN