Vibrational spectroscopic studies,conformations and ab initio calculations of 1,2‐bis(trifluorosilyl)ethane (SiF3CH2CH2SiF3)

Infrared spectra of 1,2‐bis(trifluorosilyl)ethane (SiF₃CH₂CH₂SiF₃) were obtained in the vapour and liquid phases, in argon matrices and in the solid phase. Raman spectra of the compound as a liquid were recorded at various temperatures between 293 and 270 K and spectra of an apparently crystalline solid were observed. The spectra revealed the existence of two conformers (anti and gauche) in the vapour, liquid and in the matrix. When the vapour was chock‐frozen on a cold finger at 78 K and annealed to 150 K, certain weak Raman bands vanished in the crystal. The vibrational spectra of the crystal demonstrated mutual exclusion between IR and Raman bands in accordance with C_2h symmetry. Intensity variations between 293 and 270 K of pairs of various Raman bands gave ΔH(gauche—anti) = 5.6 ± 0.5 kJ mol⁻¹ in the liquid, suggesting 85% anti and 15% gauche in equilibrium at room temperature. Annealing experiments indicate that the anti conformer also has a lower energy in the argon matrices, is the low‐energy conformer in the liquid and is also present in the crystal. The spectra of both conformers have been interpreted, and 34 anti and 17 gauche bands were tentatively identified. Ab initio and density functional theory (DFT) calculations were performed giving optimized geometries, infrared and Raman intensities and anharmonic vibrational frequencies for both conformers. The conformational energy difference derived in CBS‐QB3 and in G3 calculations was 5 kJ mol⁻¹. Copyright © 2009 John Wiley & Sons, Ltd.     

Infrared and Raman Spectra,conformations, ab initio calculations and spectral assignments of 1,3‐disilabutane (SiH3CH2SiH2CH3)

Raman spectra of 1,3‐disilabutane (SiH₃CH₂SiH₂CH₃) as a liquid were recorded at 293 K and as a solid at 78 K. In the Raman cryostat at 78 K an amorphous phase was first formed, giving a spectrum similar to that of the liquid. After annealing to 120 K, the sample crystallized and large changes occurred in the spectra since more than 20 bands present in the amorphous solid phase vanished. These spectral changes made it possible to assign Raman bands to the anti or gauche conformers with confidence. Additional Raman spectra were recorded of the liquid at 14 temperatures between 293 and 137 K. Some Raman bands changed their peak heights with temperature but were countered by changes in linewidths, and from three band pairs assigned to the anti and gauche conformers, the conformational enthalpy difference Δ_confH(gauche–anti) was found to be 0 ± 0.3 kJ mol⁻¹ in the liquid. Infrared spectra were obtained in the vapor and in the liquid phases at ambient temperature and in the solid phases at 78 K in the range 4000–400 cm⁻¹. The sample crystallized immediately when deposited on the CsI window at 78 K, and many bands present in the vapor and liquid disappeared. Additional infrared spectra in argon matrixes at 5 K were recorded before and after annealing to temperatures 20–34 K. Quantum chemical calculations were carried out at the HF, MP2 and B3LYP levels with a variety of basis sets. The HF and DFT calculations suggested the anti conformer as the more stable one by ca 1 kJ mol⁻¹, while the MP2 results favored gauche by up to 0.4 kJ mol⁻¹. The Complete Basis Set method CBS‐QB3 gave an energy difference of 0.1 kJ mol⁻¹, with anti as the more stable one. Scaled force fields from B3LYP/cc‐pVQZ calculations gave vibrational wavenumbers and band intensities for the two conformers. Copyright © 2007 John Wiley & Sons, Ltd.     

Gas‐phase structure and new vibrational study of methyl trifluoroacetate (CF3C(O)OCH3)

The molecular structure of methyl trifluoroacetate (CF₃C(O)OCH₃) has been determined in the gas phase from electron‐diffraction data supplemented by ab initio (MP2) and DFT calculations using different basis sets. Experimental data revealed an anti conformation with a dihedral angle θ (CCOC) = 180°. Quantum mechanical calculations indicate the possible existence of two conformers, differing by a rotation about the C(O) O bond. The global minimum represents a C_s‐symmetric structure in which the CF₃ group has the anti orientation with respect to the CH₃ group, but there is another potential minimum, much higher in energy, representing a C_s‐symmetric structure with a cis conformation. The preference for the anti conformation was studied using the total energy scheme and the natural bond orbital (NBO) partition scheme. Additionally, the total potential energy has been deconvoluted using a six‐fold decomposition in terms of a Fourier‐type expansion, showing that the electrostatic and steric contributions are dominant in stabilizing the anti conformer. Infrared spectra of CF₃C(O)OCH₃ were obtained for the gaseous and liquid phases, while the Raman spectrum was recorded for the liquid phase. Harmonic vibrational frequencies and a scaled force field have been calculated, leading to a final root mean‐square deviation of 9 cm⁻¹ when comparing experimental and calculated frequencies. Copyright © 2009 John Wiley & Sons, Ltd.     

Substituent effects on the conformational stability of allyl fluorides

By the B3P86/6‐311G(3d,2p) method, remote substituent effects on trans‐YCH?CHCH₂F were investigated by examining their conformational stabilities, molecular geometries, and stereoelectronic interactions in this paper. The cis conformer is favored for Y?H, Cl, Me, Vinyl, CF₃, CN, CHO, and NO₂, whereas the gauche is favored for Y?OMe, OH. A correlation of ΔH with the substituent constants σ⁺(Y) shows that the increasing electron‐withdrawing ability of the substituent Y increases the relative stability of the cis conformer. It was found that the substituent effect on the molecule stabilization energies (relative to CH₂?CHCH₂F) is more significant in the gauche conformers than in the cis conformers. In agreement, molecular structures of the gauche conformers were also observed to vary more significantly with the substitution than those of the cis conformers. By the second‐order perturbation energy (E(2)) in NBO analysis, it was found that the total C₂–C₃ vicinal hyperconjugation is determinant in the enthalpy difference and consequently controls the conformational stability. Further analysis shows that the substituent effect on the C₂–C₃ vicinal hyperconjugations is much higher in the gauche conformers than in the cis conformers. The highly sensitive π_C?C→σ*_{C? F} interaction to the substitution in the gauche conformers, is the leading factor in variation of molecular stability and geometry. Copyright © 2010 John Wiley & Sons, Ltd.     

Conformational,vibrational, and structural studies of 2,2,3,3,3‐pentafluoropropylamine from Raman and infrared spectra of gas,liquid, xenon solutions,and solid supported by ab initio calculations

The Raman and infrared spectra (3500–50 cm⁻¹) of the gas, liquid or solution, and solid were recorded of 2,2,3,3,3‐pentafluoropropylamine (CF₃CF₂CH₂NH₂) and the ND₂ isotopomer. Variable temperature (−55 to − 100 °C) studies of the infrared spectra (3600–400 cm⁻¹) of samples dissolved in liquid xenon have been carried out. From these data, two of the five possible conformers have been identified and their relative stabilities obtained. The enthalpy difference was determined between the more stable Tt conformer and the less stable Tg form to be 280 ± 14 cm⁻¹ (3.35 ± 0.17 kJ/mol). The first indicator is the NCCC dihedral angle (G = gauche or T = trans), and the second one (g = gauche or t = trans) is the relative position of the lone pair of electrons on nitrogen with respect to the β‐carbon. The percentage of the Tg conformer at ambient temperature is estimated to be 34 ± 2%. The conformational stabilities have been predicted from ab initio calculations utilizing several different basis sets up to aug‐cc‐pVTZ for both MP2(full) and density functional theory calculations by the B3LYP method. Vibrational assignments have been provided for most of the observed bands for both isotopomers, supported by MP2(full)/6‐31G(d) ab initio calculations to predict the harmonic force fields, wavenumbers, infrared intensities, Raman activities, and depolarization ratios for both conformers. Estimated r₀ structural parameters were obtained from adjusted MP2(full)/6‐311 + G(d,p) calculations. The results are discussed and compared with the corresponding properties of some related molecules. Copyright © 2011 John Wiley & Sons, Ltd.     

Vibrational spectra of 2, 3 and 2, 6 dichloro anilines

The infrared and laser Raman spectra of 2, 3 dichloro aniline and 2, 6 dichloro aniline have been recorded. The vibrational spectra have been analysed assumingC _s andC _2v point groups for 2, 3 dichloro aniline and 2, 6 dichloro aniline respectively. Assignments for fundamental vibrations, combination and overtone frequencies and internal modes of vibration of amino group have been proposed.     

A comprehensive study of (CH3)2CHOC(S)SC(O)OCH3 using matrix isolation technique,X‐ray analysis,spectroscopic studies and theoretical calculations

Potassium isopropyl xanthate, (CH₃)₂CHOC(S)SK, reacts with methyl chloroformiate ClC(O)OCH₃ to yield (methoxycarbonyl) (2‐propoxythiocarbonyl) sulfide, (CH₃)₂CHOC(S)SC(O)OCH₃. This novel xanthogen formate was characterized by ¹H and ¹³C{¹H} NMR spectroscopy, mass spectrometry and IR and Raman spectroscopy. The structure of a single crystal of (CH₃)₂CHOC(S)SC(O)OCH₃ was determined by X‐ray diffraction analysis at 173 K. The conformational properties have been studied by liquid IR and Raman spectroscopy, matrix isolation spectroscopy together with photochemical studies and quantum chemical calculations (HF and B3LYP methods with the 6‐31+G* basis set). The analysis of the IR spectrum of liquid (CH₃)₂CHOC(S)SC(O)OCH₃ suggests the presence of two conformers in equilibrium at room temperature. However, in the photochemical matrix study, an equilibrium of three conformers was detected. These forms were further characterized by theoretical calculations. Different photolysis products, such as CH₃OC(O)SCH(CH₃)₂, OCS, CO, CO₂ and CS₂, were identified by matrix spectroscopy. The IR absorptions of CH₃OC(O)SCH(CH₃)₂, for which literature data are scarce, were analysed in the light of the results of appropriate theoretical calculations. Copyright © 2009 John Wiley & Sons, Ltd.     

An experimental and quantum-chemical study of the Raman spectra and rotational isomerism of thiophosphites (RS) n PCl3 − n (R = Me, Et; n = 1, 2)

The Raman spectra of different conformations of CH₃SPCl₂, C₂H₅SPCl₂, and (C₂H₅S)₂PCl are studied within the framework of the density functional theory (B3LYP/6-31G* and B3LYP/6-31+G*) using the method of scaling of force fields. Comparison of the calculated and experimental spectra makes it possible to interpret the latter and to establish the existence of trans and gauche conformers of these molecules, which are formed due to internal rotation about the P-S and S-C bonds. This comparison also shows that, for the prediction of the degrees of depolarization of Raman lines to be correct, it is necessary to introduce diffuse functions into the basis set.     

Vibrational Spectra of Dimethyldithiophosphinate Anion: (CH3)2PS2

Abstract

The infrared and Raman spectra of dimethyldithiophosphinate anion (CH₃)₂PS₂ were measured and the vibrational modes for the anion complex were assigned. A Normal Coordinate Analysis in the Modified General Valence Force Field (MGVFF) approximation was carried out assuming C_2v symmetry. Ab Initio Calculations at RHF and MP2 level were also carried out for the anion geometry as well as for its frequencies, intensities and force constants.     

Conformational and structural studies of n‐propylamine from temperature dependent Raman and far infrared spectra of xenon solutions and ab initio calculations

The Raman and infrared spectra (4000 to 50 cm^–1) of the gas, liquid or solution, and solid have been recorded of n‐propylamine, CH₃CH₂CH₂NH₂. Variable temperature (−60 to −100 °C) studies of the Raman (1175 to 625 cm^–1) and far infrared (600 to 10 cm^–1) spectra dissolved in liquid xenon were carried out. From these data, the five possible conformers were identified and their relative stabilities obtained with enthalpy difference relative to trans–trans (Tt) for trans–gauche (Tg) of 79 ± 9 cm^–1 (0.9 ± 0.1 kJ/mol); for Gg of 91 ± 26 cm^–1 (1.08 ± 0.3 kJ/mol); for Gg′ of 135 ± 21 cm^–1 (1.61 ± 0.2 kJ/mol); for Gt of 143 ± 11 cm^–1 (1.71 ± 0.1 kJ/mol). The percentage of the five conformers is estimated to be 18% for the Tt, 24 ± 1% for Tg, 23 ± 3% for Gg, 18 ± 1% for Gg′ and 18 ± 1% for Gt at ambient temperature. The conformational stabilities have been predicted from ab initio calculations utilizing several different basis sets up to aug‐cc‐pVTZ from both second‐order Møller–Plesset (MP2, full) and density functional theory calculations by the Becke, three‐parameter, Lee–Yang–Parr method. Vibrational assignments were provided for the observed bands for all five conformers, which are supported by MP2(full)/6‐31G(d) ab initio calculations to predict harmonic force constants, wavenumbers, infrared intensities, Raman activities and depolarization ratios for both conformers. Estimated r₀ structural parameters were obtained from adjusted MP2(full)/6‐311+G(d,p) calculations. The results are discussed and compared with the corresponding properties of some related molecules. Copyright © 2012 John Wiley & Sons, Ltd.     

The microwave spectra of symmetric top polyacetylenes: 1,3,5-Heptatriyne,CH3(CC)3H and 1-cyano-2,4-pentadiyne,CH3(CC)2CN

The rotational spectra of 1,3,5-heptatriyne, CH₃(CC)₃H and 1-cyano-2,4-pentadiyne, CH₃(CC)₂CN have been studied in detail between 26.5 and 40.0 GHz. The molecules have long linear chains of heavy atoms and show characteristic C_3v symmetric top spectra consisting of groups of R-branch lines at regular intervals separated by approximately 2B₀. Six isotopic modifications of CH₃(CC)₂CN have been detected in natural abundance allowing r_s substitution structural data to be derived for this species. Long linear polyacetylenic chains are quite flexible and this dynamic property manifests itself in the appearance of extended sequences of complex vibrational satellites associated with the bending of the chain. The vibrational ground state spectra as well as several low frequency vibrational satellites have been analyzed yielding various vibration-rotation parameters. For CH₃(CC)₃H B₀ = 778.2445 ± 0.0007 and for CH₃(CC)₂CN B₀ = 778.040 ± 0.001 MHz.     

Structures and thermochemistry of methyl ethyl sulfide and its hydroperoxides: HOOCH2SCH2CH3, CH3SCH(OOH)CH3, CH3SCH2CH2OOH,and radicals

Hydroperoxides and the corresponding peroxy radicals are important intermediates during the partial oxidation of methyl ethyl sulfide (CH₃SCH₂CH₃) in both atmospheric chemistry and in combustion. Structural parameters, internal rotor potentials, bond dissociation energies, and thermochemical properties (ΔH_f^o, S^o and C_p(T)) of 3 corresponding hydroperoxides CH₂(OOH)SCH₂CH₃, CH₃SCH(OOH)CH₃, CH₃SCH₂CH₂OOH of methyl ethyl sulfides, and the radicals formed via loss of a hydrogen atom are important to understanding the oxidation reactions of MES. The lowest energy molecular structures were identified using the density functional B3LYP/6‐311G(2d,d,p) level of theory. Standard enthalpies of formation (ΔH_f^o₂₉₈) for the radicals and their parent molecules were calculated using the density functional B3LYP/6‐31G(d,p), B3LYP/6‐31 + G(2d,p), and the composite CBS‐QB3 ab initio methods. Isodesmic reactions were used to determine ?H_f^o values. Internal rotation potential energy diagrams and rotation barriers were investigated using the B3LYP/6‐31G(d,p) level theory. Contributions for S^o₂₉₈ and C_p(T) were calculated using the rigid rotor harmonic oscillator approximation based on the structures and vibrational frequencies obtained by the density functional calculations, with contributions from torsion frequencies replaced by internal rotor contributions. The recommended values for enthalpies of formation of the most stable conformers of CH₃SCH₂CH_2, CH₂(OOH)SCH₂CH₃, CH₃SCH(OOH)CH₃, and CH₃SCH₂CH₂OOH are ?14.0, ?33.0, ?37.2, and ?32.7 kcal/mol, respectively. Group additivity values were developed for estimating properties of structurally similar and larger sulfur‐containing peroxides. Groups for use in group additivity estimation of sulfur peroxide thermochemical properties were developed.     

The assignment of Co-C bond stretching vibrational frequency of CH3Co(DH)2H2O in IR and Raman spectra

Abstract

In order to aid assignment of Co-C bond stretching vibrational frequency of CH₃Co(DH)₂H₂O (DH=dimethylgIyoximato monanion) in IR and Raman spectra, its isotopic substitution CD₃Co(DH)₂H₂O has been synthesized and normal coordinate analyses on the two complex have been made. The bands were assigned in terms of potential energy distribution. The results provide definitive band assignment of the Co-C bond and Co-N bond stretching modes which are coupling at 511 cm^?1.     

Vibrational and Conformational Analysis of 2-Methyl-1-butene

Normal coordinate calculations were made for 2-methyl-1-butene to aid in making vibrational assignments for both conformers. A partial solid-state IR spectrum was obtained that showed the presence of only the trans (C_s) conformer. Molecular mechanics and semi-empirical molecular orbital calculations were also made for both conformers.     

Vibrational spectroscopy and DFT calculations of N,N′‐dicyclohexylcarbodiimide

Infrared (IR) and Raman spectra were obtained for N,N′‐dicyclohexylcarbodiimide (DCC) in the solid state and in CHCl₃ solution. Structures and vibrational spectra of isolated, gas‐phase DCC molecules with C₂ and C_i symmetries, computed at the B3‐LYP/cc‐pVTZ level, show that the IR and Raman spectra provide convincing evidence for a C₂ structure in both the solid state and in CHCl₃ solution. Using a scaled quantum‐chemical force field, these density functional theory calculations have provided detailed assignments of the observed IR and Raman bands in terms of potential energy distributions. Comparison of solid‐state and solution spectra, together with a Raman study of the melting behaviour of DCC, revealed that no solid‐state effects were evident in the spectra. Copyright © 2010 John Wiley & Sons, Ltd.     

Vibrational and Conformational Analysis of 5-Methyl-2-Hexyne

Infrared and Raman spectra were obtained for 5- methyl-2-hexyne and wereinterpreted with the aid of normal coordinate calculations. The spectra and molecular mechanics calculations show the compound to exist in two spectroscopically distinguishable stable conformations, with the C₁ conformer being only a little more stable than the C_s, conformer. Vibrational assignments were made for both conformers.     

Electro-optical parameters and Raman intensities of CH4, CH3D,CH2D2, CHD3 and CD4

The absolute Raman intensities and the depolarization ratios of the vibrational bands of gaseous CH₄, CH₃D, CH₂D₂, CHD₃ and CD₄ have been computed here using a compact formulation of the bond polarizability theory, in its zero and first-order approximations. The agreement with experimental values taken from the literature is very good for the first-order approximation, although the difference between both approximations is not very large for these molecules. The derivatives of the polarizability with respect to the symmetry coordinates of methane are given with signs that are physically meaningful.     

Spectroscopic and ab initio characterization of the conformational states of the bis(perfluoro‐ ethanesulfonyl)imide anion (BETI−)

Ab initio calculations were combined with infrared and Raman studies to spectroscopically distinguish the two conformers of the BETI⁻ or bis(perfluoroethanesulfonyl)imide anion, [N(SO₂C₂F₅)₂]⁻, as was previously done for [N(SO₂CF₃)₂]⁻, the TFSI⁻ anion. BETI⁻ is predicted to exist, as does TFSI⁻, in two conformational states of C₂ and C₁ symmetries, the former being more stable by about 6 kJ mol⁻¹. This conformational isomerism produces weak Raman splittings that can be resolved only at low temperatures. Thus, solutions of LiBETI with glymes cooled down to 113 K exhibit a very intense Raman doublet at ∼745–740 cm⁻¹ characteristic of a quenched conformational equilibrium between the C₂ and C₁ conformers. Annealing of the (G3)₂:LiBETI solvate, where G3 is triglyme, leads to an ordered crystalline phase with all the anions in the C₂ conformation, as in the reference salt Me₄NBETI. This conclusion cannot be extended to all the systems in which the BETI⁻ anion interacts weakly with the cation, however, since the diglyme solvate, (G2)₂:LiBETI, contains both C₁ and C₂ anion conformers (in 2:1 ratio) at low temperatures independent of the sample's thermal history. The conformational splittings are larger in infrared, as illustrated by two absorption bands at 601 and 615 cm⁻¹ associated with the C₂ and C₁ anion conformers, respectively. It is possible to follow the relative intensities of these bands in a LiBETI solution with diglyme above room temperature up to 387 K. The C₂ conformer is found to be more stable than C₁ by 4.7 ± 0.7 kJ mol⁻¹. Copyright © 2006 John Wiley & Sons, Ltd.     

Solvent‐dependent structural dynamics of 2(1H)‐pyridinone in light absorbing S4(ππ*) state

The B‐band resonance Raman spectra of 2(1H)‐pyridinone (NHP) in water and acetonitrile were obtained, and their intensity patterns were found to be significantly different. To explore the underlying excited state tautomeric reaction mechanisms of NHP in water and acetonitrile, the vibrational analysis was carried out for NHP, 2(1D)‐pyridinone (NDP), NHP–(H₂O)_n (n = 1, 2) clusters, and NDP–(D₂O)_n (n = 1, 2) clusters on the basis of the FT‐Raman experiments, the B3LYP/6‐311++G(d,p) computations using PCM solvent model, and the normal mode analysis. Good agreements between experimental and theoretically predicted frequencies and intensities in different surrounding environments enabled reliable assignments of Raman bands in both the FT‐Raman and the resonance Raman spectra. The results indicated that most of the B‐band resonance Raman spectra in H₂O was assignable to the fundamental, overtones, and combination bands of about ten vibration modes of ring‐type NHP–(H₂O)₂ cluster, while most of the B‐band resonance Raman spectra in CH₃CN was assigned to the fundamental, overtones, and combination bands of about eight vibration modes of linear‐type NHP–CH₃CN. The solvent effect of the excited state enol‐keto tautomeric reaction mechanisms was explored on the basis of the significant difference in the short‐time structural dynamics of NHP in H₂O and CH₃CN. The inter‐molecular and intra‐molecular ESPT reaction mechanisms were proposed respectively to explain the Franck–Condon region structural dynamics of NHP in H₂O and CH₃CN.Copyright © 2015 John Wiley & Sons, Ltd.     

The Raman,Infrared and Proton NMR Spectra and the Structures of Dimethyl Chalcogenides

The vibrational bands of dimethyl chalcogenides (CH₃-X-CH₃) (X = O,S,Se,Te) have been assigned on the basis of C_2V symmetry by most of previous workers.^1–13) On the other hand, some ones have assigned D^3d to these molecules ^14–15) and to structurally related compounds; SiH₃-O-SiH₃ ¹⁶), CH₃-Hg-CH₃ ¹⁷), CF₃-Hg-CF₃ ¹⁸) and Cl₃Si-O-SiCl₃ ¹⁹). The symmetry of ethane(CH₃-CH₃) is obviously D_3d ²⁰⁾, because the vibrational spectra which indicate the lack of coincidence between Raman and infrared frequencies can be explained based upon D_3d symmetry, and the bent c c should theoretically be impossible. The CH₃-X-CH₃ molecules are considered as a derivative in which CH₃ group is connected to CH₃ in opposite direction along the z axis and x atom is inserted between the two CH₃ groups. Consequently, for a linear C-X-C model, the vibrational spectra of CH₃-X-CH₃ ^14,15) should be similar to those of CH₃-CH₃, except being added C-O-C stretching and bending bands. The obtained spectra of CH₃-X-CH₃ ^14,15) show a marked correspndence to that of ethane, and indicate that the rule of mutual exclusion holds between Raman and infrared frequencies. Therefore the symmetry of CH₃-X-CH₃ Seems to be D_3d, But mst of the previom papers ^1–13) have assigned C_2v to CH₃-X-CH₃ as mentioned above.