Structural, conformational and vibrational properties of 1,1,1-Trifluoro-N-(1,1,2,2,2-pentafluoroethyl) methanesulfinimidoyl chloride, CF3CF2NS(Cl)CF3

The structural, conformational, and configurational properties of 1,1,1-Trifluoro-N-(1,1,2,2,2-pentafluoroethyl) methanesulfinimidoyl chloride, CF3CF2NS(Cl)CF3 have been studied by vibrational spectroscopy [IR (vapor) and Raman (liquid)] and quantum chemical calculations [B3LYP, MP2 and B3PW91 levels of theory using the 6-311+G(d), 6-311+G(df) and 6-311+G(2df) basis sets]. According to these theoretical approximations, CF3CF2NS(Cl)CF3 exists in the gas phase as a mixture of a favored anticlinal form (CN bond anticlinal with respect to the CSCl bisector) with C1 symmetry and a less abundant syn conformer showing C1 symmetry as well (ΔG° ≈ 1.20 kcal mol-1). Due to the small contribution only a few corresponding vibrational modes of the syn conformer could be assigned confidently in the experimental spectra. Compared to CF3CF2NS(F)CF3, the replacement of F by Cl produces a clear change in NS bond length and the corresponding stretching frequency, without affecting the conformational properties.Fil: Robles, Norma Lis. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química Física; ArgentinaFil: Chemes, Doly María. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química Física; ArgentinaFil: Heinz Oberhammer. Eberhard Karls Universität Tübingen; AlemaniaFil: Cutin, Edgardo Hugo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química Física; Argentin

Assessment of the molecular structure and spectroscopic properties of CF3-substituted sulfinylaniline derivatives

The presence of a perfluorinated functional group as a substituent of the aromatic ring in m- and o-trifluoromethylsulfinylaniline may provide conformational and vibrational properties of interest for the synthesis of compounds of pharmacological relevance, as it was observed for other N-sulfinylaniline derivatives previously reported. The air sensitive and highly reactive compounds under study were prepared by the reaction of the corresponding aniline derivatives and thionyl chloride. The liquid samples were characterized by FT IR, Raman and NMR (1H and 13C) spectroscopies and GC/MS spectrometry. The experimental spectra indicate the presence of a single conformer of syn geometry (syn of the C-N bond with respect to the S=O bond), in good agreement with results obtained by quantum chemical calculations derived from the Functional Density Theory. The stable conformation found as the global minimum of the potential energy surface was rationalized by considering intramolecular orbital interactions evinced by a Natural Bond Orbital (NBO) analysis and the quantum theory of Atoms In Molecules (AIM). Through this last approach, an intramolecular C-H⋅⋅⋅O interaction meeting the characteristics of an anti-hydrogen bond was found.Fil: Chemes, Doly María. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico - CONICET - Tucumán. Unidad de Administración Territorial; ArgentinaFil: Lezama, José Osvaldo Guy. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; ArgentinaFil: Cutin, Edgardo Hugo. Universidad Nacional de Tucumán. Facultad de Ciencias Exactas y Tecnología; Argentina. Universidad Nacional de Tucumán. Instituto de Biotecnología Farmacéutica y Alimentaria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Biotecnología Farmacéutica y Alimentaria; ArgentinaFil: Robles, Norma Lis. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentin

First example of a preferred anti configuration in RN=SX<SUB>2</SUB> compounds: N-fluoroformyliminotrifluoromethylsulfur fluoride, FC(O)N=S(F)CF<SUB>3</SUB>

The vibrational spectra, including Raman spectra at different temperatures and resonance Raman spectra, and theoretical calculations of N‐fluoroformyliminotrifluoromethylsulfur fluoride, FC(O)N= S(F)CF3, were obtained and interpreted. They point to the existence of a predominant anti–syn form and in equilibrium at lower concentration a syn–syn form (the first related to the nitrogen lone pair with respect to the sulfur lone pair and the second is related to the C= O double bond with respect to the N= S double bond). The general result indicates that it is the first anti configuration reported for this type of molecule implying for the energetically most favoured form an anti configuration of the lone pairs attached to both the S and N atoms.Centro de Química Inorgánic

On the search of the influence of substituents in the structural and vibrational properties of p-substituted sulfinylanilines: Study of p-trifluoromethylsulfinylaniline

The study of substitution effects on the structural and vibrational properties of para substituted sulfinylanilines proceeds a step forward with the study of p-trifluoromethylsulfinylaniline, synthesized and characterized by NMR, Raman, FTIR and mass spectra. The experimental spectra were compared and analyzed taking into account theoretical spectra obtained with quantum chemical calculations at different levels of theory. The spectroscopic results reveal the presence of a single form of this molecule which, according to the calculated molecular structure, possesses the NSO group coplanar with the ring plane. In addition, the syn conformation of the NSO group is also derived from both, experimental and theoretical data. The presence of the CF 3 group in the para position of the aromatic ring influences the properties of the N[dbnd]S[dbnd]O group, with the N[dbnd]S bond more strongly affected than the S[dbnd]O bond compared to results reported for other para substituted sulfinylanilines.Fil: Chemes, Doly María. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán; Argentina. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química Física; ArgentinaFil: Cutin, Edgardo Hugo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán; Argentina. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química Física; ArgentinaFil: Alvarez, Rosa Maria Susana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina. Universidad Nacional de Tucumán. Facultad de Ciencias Exactas y Tecnología; ArgentinaFil: Robles, Norma Lis. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina. Universidad Nacional de Tucumán. Facultad de Ciencias Exactas y Tecnología; ArgentinaFil: Oberhammer, Heinz. Universität Tübingen; Alemani

Synthesis, experimental and theoretical characterization of m-fluorosulfinylaniline

The synthesis of m-fluorosulfinylaniline together with a tentative assignment of the vibrational, NMR and mass spectra are reported. Quantum chemical calculations predict two stable conformers, with very similar energies, both of which possess in the liquid phase syn structure of the -N[double bond, length as m-dash]S[double bond, length as m-dash]O moiety (syn of the S[double bond, length as m-dash]O double bond relative to the C-N single bond). Both conformers belong to the CS symmetry group and differ by the relative orientation of the fluorine atom and the NSO group. However, the FT-IR, FT-Raman and NMR spectra do not allow a distinction between these two conformers. The experimentally observed spectral data (FT-IR, FT-Raman, 1H and 13C and GC-mass spectrometry) of the title compound are compared with the spectral data obtained by quantum chemical calculations and the gauge including atomic orbital (GIAO) method (DFT/B3LYP approximation using 6-311+G(df), 6-311++G(df,pd) and cc-pVTZ basis sets). Moreover, natural bond orbital (NBO) analysis is applied for studying the stability of the molecule upon charge delocalization in order to provide an explanation of its electronic properties.Fil: Paez Jerez, Ana Laura. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Tucumán. Instituto de Quimica del Noroeste; Argentina. Universidad Nacional de Tucumán; ArgentinaFil: Chemes, Doly María. Universidad Nacional de Tucuman. Facultad de Bioquimica, Quimica y Farmacia. Instituto de Quimica Fisica; ArgentinaFil: Cutin, Edgardo Hugo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Tucumán. Instituto de Quimica del Noroeste; Argentina. Universidad Nacional de Tucumán; ArgentinaFil: Oberhammer, Heinz . Universität Tübingen. Institut für Physikalische und Theoretische Chemie; AlemaniaFil: Robles, Norma Lis. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Tucumán. Instituto de Quimica del Noroeste; Argentina. Universidad Nacional de Tucumán; Argentin

Synthesis, characterization and vibrational studies of p-chlorosulfinylaniline

p-Cholorosulfinylaniline was prepared by the reaction of p-chloroaniline and SOCl2. The structural, conformational and configurational properties of the obtained liquid compound were studied by Raman and infrared spectroscopy in the liquid state. The assignment of the vibrational spectra was carried out with the help of data obtained by quantum chemical calculations at the harmonic oscillator approximation and using anharmonic vibrational self-consistent field (VSCF) method as well. The 1H and 13C NMR chemical shifts of the molecule were calculated by Gauge including orbital (GIAO) method (DFT/B3LYP approximation using 6-311 + G (df), 6-311++G (df,pd) and cc-pVTZ basis sets) and compared to the experimental values. Natural Bond Orbital analysis provides an explanation of the stability of the molecule and its electronic properties upon charge delocalization.Fil: Chemes, Doly María. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia; ArgentinaFil: Alonso de Armiño, Diego Javier. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia; ArgentinaFil: Cutin, Edgardo Hugo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; ArgentinaFil: Oberhammer, Heinz. Universitat Tübingen; AlemaniaFil: Robles, Norma Lis. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentin

Gas phase structure of ((fluoroformyl)imido)sulfuryl difluoride, FC(O)N=S(O)F2

The geometric structure and conformational properties of gaseous ((fluoroformyl)imido) sulfuryl difluoride, FC(O)N{double bond, short}S(O)F2, was investigated by gas electron diffraction (GED) and quantum chemical methods (MP2 and B3LYP with 6-31G(d) and 6-311+G(2df) basis sets). In combination with earlier reported infrared spectra, the GED study results in a mixture of at least three conformers, 71(10)% syn(N{double bond, short}S)-syn(N-C), 14(8)% anti(N{double bond, short}S)-syn(N-C) and 15(5)% syn(N{double bond, short}S)-anti(N-C). Syn(N{double bond, short}S) or anti(N{double bond, short}S) implies synperiplanar or anticlinal orientation of the FC(O) group with respect to the SF2 bisector and syn(N-C) or anti(N-C) implies synperiplanar or antiperiplanar orientation of the C{double bond, short}O bond with respect to the N{double bond, short}S bond. The anti(N{double bond, short}S)-anti(N-C) conformer has not been observed, but a small amount (<5%) cannot be excluded. These conformational properties are well reproduced by quantum chemical calculations with small basis sets and the geometric parameters are reproduced satisfactorily with large basis sets.Fil: Robles, Norma Lis. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; ArgentinaFil: Cutin, Edgardo Hugo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química Física; ArgentinaFil: Heinz Oberhammer. Universität Tübingen; Alemani

Synthesis, spectroscopic characterization and theoretical calculations of ClF2CC(O)NPCl3 ([chloro(difluor)acetyl]phosphorimidic trichloride)

The synthesis of [chloro(difluor)acetyl]phosphorimidic trichloride (ClF2CC(O)NPCl3), together with a tentative assignment of the vibrational, NMR and mass spectra, are reported. Quantum chemical calculations (MP2 and B3LYP methods with 6-311+G(d) and 6-311+G(2df,p) basis sets) predict three stable conformers in the gas phase (syn, gauche and anti, defined according to the rotation around both the ClCCN and the CCNP dihedral angles). However, only a single C1 symmetry conformer is observed in the liquid phase, possessing the CO double bond in synperiplanar orientation with respect to the PN double bond, and the ClC bond distorted from the plane defined by the CC(O)NP entity. A Natural Bond Orbital (NBO) analysis was carried out for the title compound and related molecules in order to provide an explanation about the electronic properties.Fil: Iriarte, Ana Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Cutin, Edgardo Hugo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; ArgentinaFil: Argüello, Gustavo Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentin

CF3CF2N=S(F)CF3: Vibrational spectra and conformational properties

The structural, conformational, and configurational properties of 1,1,1-trifluoro-N-(1,1,2,2,2-pentafluoroethyl) methanesulfinimidoyl fluoride, CF3CF2N=S(F)CF3 have been studied by vibrational spectroscopy [IR (vapor) and Raman (liquid)] and quantum chemical calculations [B3LYP, MP2 and B3PW91 levels of theory (using the 6-311+G(d) and 6-311+G(2df) basis sets). According to these theoretical approximations,CF3CF2N=S(F)CF3 might be found in the gas phase as a mixture of a favoured anticlinal form (CAN bond anticlinal with respect to the CASAF bisector angle) and a less abundant syn conformer showing C1 symmetry as well (DG 1.5 kcal mol1). However, corresponding vibrational modes for these conformers show only small shifts which would not allow confidently detecting the rather small contribution of this second form in the experimental spectra.Fil: Robles, Norma Lis. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Tucumán. Instituto de Quimica del Noroeste; Argentina. Universidad Nacional de Tucumán; ArgentinaFil: Oberhammer, Heinz . Universität Tübingen; AlemaniaFil: Mews, Rüdiger . Universitat Bremen; AlemaniaFil: Cutin, Edgardo Hugo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Tucumán. Instituto de Quimica del Noroeste; Argentina. Universidad Nacional de Tucumán; Argentin

(1,1-Dichloro-2,2,2-trifluoroethylimino) sulfur dichloride, CF3CCl2N=SCl2: Vibrational spectra and quantum chemical calculations

The vibrational spectra of (1,1-dichloro-2,2,2- trifluoroethylimino)sulfur dichloride, CF3CCl2N@SCl2, were recorded in the gas phase with IR spectroscopy and in the liquid state with Raman spectroscopy. Quantum chemical calculations at the HF, B3LYP (6-311+G(d) and 6-311+G(2df) basis sets) and MP2 levels of theory (6-31+G(d) and 6-311+G(df) basis sets) were performed. According to all calculations the lowest energy conformer possesses C1 symmetry with syn orientation of the SCl2 group relative to the N-C bondand near-trans orientation of the CF3 group relative to the N=S bond. Calculations predict the presence of a second stable conformer with anticlinal orientation of the SCl2 group which, however, possesses considerably higher energy and is therefore not observed in the analysis of the experimental vibrational spectra. The vibrational spectra were assigned for a single conformer in accordance with these calculations.Fil: Flores Antognini, Andrea. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; ArgentinaFil: Cutin, Edgardo Hugo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; ArgentinaFil: Robles, Norma Lis. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; ArgentinaFil: Oberhammer, Heinz. Universität Tübingen; Alemani