Infrared and electronic absorption spectra of some trisubstituted benzenes

The electronic absorption spectra of 2,3-, 2,4-, 2,5-, 2,6- and 3,4-difluorobenzonitriles, 3,4-difluoroaniline and 3,4-difluoroanisole in the ultraviolet region in vapour phase have been recorded on medium quartz and Hilger large quartz spectrographs and on a Hitachi model 150-20 UV-VIS ratio recording spectrophotometer. All the molecules investigated have exhibited two π* ← π band systems corresponding to ¹B_2u ← ¹A_1g (λ2600 Å) and ¹B_1u ← ¹A_1g (λ2100 Å) systems of benzene. The infrared absorption spectra of all the molecules studied have also been recorded and analysed. These infrared data have been taken to help analyse the u.v. spectra of the molecules studied.     

Complex hydrogen bonded cations-IV further symmetric ions

Solutions containing the complex hydrogen bonded cations (NMe imidazole)₂ H⁺; (thiazole)₂H⁺ and (benzothiazole)₂H⁺ have been prepared. The spectra display a pronounced double maximum in the v_s infrared band, which is replaced by a single band in the D-bridged analogues. The activity of the far infrared v_s band, the frequency of the NH bending mode, and the observation of internal modes characteristic of both donor and acceptor all indicate that the hydrogen bonding proton is not located at the mid point of the NβN bridge.Salts of the complex (benzothiazole)₂H⁺ cation have been obtained in the solid state, and have a similar infrared spectrum to the complex in solution.     

Spectra and structure of phosphorus—boron compounds—XXVI. Infrared and Raman spectra,conformational stability and normal coordinate analysis of ethyldichlorophosphine-borane

The Raman (3500-10 cm⁻¹) and infrared (3500-50 cm⁻¹) spectra of solid ethyldichlorophosphine-borane, CH₃CH₂P(BH₃)Cl₂ and its deuterated analog, CH₃CH₂P(BD₃)Cl₂ have been recorded. Additionally, the infrared spectra of the gases and the Raman spectra of the liquids have been recorded and qualitative depolarization ratios have been obtained. Based on the fact that several distinct Raman lines disappear on going from the liquid to the solid state, it is concluded that the molecule exists as a mixture of the gauche and trans conformers, with the trans conformer being more stable in the liquid phase, and the only one present in the solid phase. From a temperature study of the Raman spectrum of the liquid, the enthalpy difference between the gauche and trans conformers was determined to be nearly zero. Based on Raman depolarization data, group frequencies, isotopic shift factors and infrared band contours, a complete vibrational assignment has been proposed for the trans conformer. The assignment is supported by a normal coordinate calculation which was carried out utilizing a modified valence force field to obtain the frequencies of the normal modes and the potential energy distribution. The BH₃ torsion has been observed at 188 cm⁻¹, while the BD₃ torsion was not observed. The methyl torsions in the spectra of the solids have been observed at 209 and 202 cm⁻¹ for the “light” and deuterated species, respectively. From the torsional data, barriers to internal rotation have been calculated. The asymmetric torsional mode has been observed for the trans conformer in the infrared spectra of the gas phase at 108 and 104 cm⁻¹ for the BH₃ and BD₃ species, respectively. These results are compared with similar quantities for some corresponding organophosphine—borane compounds.     

Integrated absorption intensities of haloethanes and halopropanes

The infrared absorption intensities of the chlorofluorocarbons C₂Cl_xF_y, (x + y = 6); the hydrofluorocarbons C₂H_xF_yH (x + y = 6); and a number of hydrochlorofluorocarbons, including some members of the propane series, have been measured. Absorption intensities have been obtained by integration over specified ranges of frequencies. The ranges used include the atmospheric window (1250t-833 cm⁻¹), 3500-450 cm⁻¹, 1300-700 cm⁻¹, and those for selected individual absorption bands. Comparisons of the results have been made with published work where available, and attention is drawn to possible sources of error in the measurement of band areas. The spectra of the halopropanes have been included for the range 3500-150 cm⁻¹. A preliminary study has been made of the relation between the number of fluorine atoms in the molecule and the intensity of absorption of the CF stretching vibrations.     

Vibrational spectra and molecular symmetry of tetrasilylhydrazine and tetrasilylhydrazine-d12

The Raman spectra of tetrasilylhydrazine and tetrasilylhydrazine-d₁₂ have been recorded for the gas, liquid and solid phases from 25 to 2500 cm^?1. The infrared spectra of N₂(SiH₃)₄ and N₂(SiD₃)₄ have been recorded for the gas and solid phases from 40 to 2500 cm^?1. The vibrational data have been interpreted on the basis of a twisted (D_2d) molecular configuration for both the fluid and solid states.     

Electronic absorption spectrum of copper formate tetrahydrate

Single crystals of copper formate tetrahydrate were grown at room temperature. Spectra in the near infrared at room temperature and in the visible at room and liquid air temperatures were recorded on a Unicam SP-700 spectrophotometer and Hilger medium quartz spectrograph respectively. The observed absorption bands have been attributed to an ion of Cu²⁺ in tetragonal symmetry with ²B_1g as the ground state. Taking into consideration the spin—orbit coupling associated with the tetragonal field, a successful interpretation of all the observed bands has been made. The band observed in the near infrared at 11000 cm^?1 has been indentified with a vibrational overtone mode of CO₂. The crystal parameters derived are Dq = ?1380 cm^?1, Ds = ?1950 cm^?1, Dt = ?205 cm^?1 and λ = ?830 cm^?1.     

Infrared and Raman spectra and normal coordinate calculations for methylisothiocyanate

The infrared spectra (3200-50 cm^?1) of gaseous and solid CH₃NCS and CD₃NCS and the Raman spectra (3200-10 cm^?1) of the liquids and solids have been recorded. The spectra have been interpreted on the basis of a “pseudo-symmetric top” with C_3v symmetry. An assignment of the fundamental vibrations in both molecules, based on their infrared band contours, depolarization values and group frequencies, is given and discussed. Particularly interesting is the low-frequency region where band maxima were observed at 152 and 80 cm^?1 for CH₃NCS and 139 and 71 cm^?1 for CD₃NCS in the infrared spectra of the gases. A normal coordinate analysis has also been carried out based on C_3v symmetry. Considerable mixing was found between the C_αN stretch and NCS symmetric stretch in both isotopic species. The other normal modes in CH₃NCS are reasonably pure but, for the CD₃NCS molecule, considerable mixing was found between the CD₃ stretches and NCS antisymmetric stretch. The proposed vibrational assignment and the results of the normal coordinate calculations are discussed and compared with the results obtained for similar molecules.     

A reinvestigation of the vibrational spectra of cyclooctatetraene and cyclooctatetraene-d8

Band shapes in the gas phase infrared spectrum of cyclooctatetraene (COT) have been recorded in the 3500–250 cm⁻¹ range. With these and the existing vibrational data for COT and COT-d₈, revised assignments of the fundamental modes have been made for both compounds. A normal coordinate analysis based on D_2d symmetry has been carried out and used to support the vibrational assignments.     

Infrared,Raman and NMR spectra,conformational stability,and ab initio calculations of divinylmethoxyborane

The infrared spectra (4000–50 cm⁻¹) of gaseous and solid divinylmethoxyborane, (CH₂=CH)₂BOCH₃, as well as the Raman spectra (3500–20 cm⁻¹) of the liquid and solid have been recorded. Qualitative depolarization values have been obtained from the Raman spectrum of the liquid. All normal modes, except the torsions, have been assigned based on infrared band contours, depolarization values, group frequencies, and normal coordinate calculations. From a comparison of the spectra in the fluid and solid states, it is concluded that the molecule exists predominantly in a single conformation in all physical states. Frequencies and potential energy distributions for the normal modes have been calculated with the 3–21G basis set. A comparison of these calculated frequencies to the observed spectra is consistent with the predominant form having a “planar” heavy atom skeleton with C_s, symmetry. From the variable low temperature ¹³C NMR data, a barrier to rotation about the B-O bond of 10.1 ± 0.1 kcal mol⁻¹ has been determined, which is in excellent agreement with a barrier of 8.5 kcal mol"1 obtained from ab initio calculations. Structural parameters, conformational stability, and barriers to internal rotation have been obtained from ab initio Hartree-Fock gradient calculations employing both the 3–21G and 6–31G^* basis sets. The results are compared to the corresponding data for some similar organoboranes.     

Raman spectra of gases: XIV. Hexachlorodisiloxane

The Raman spectra (50–1200 cm^?1) of gaseous, liquid, and solid (Cl₃Si)₂O have been recorded. The infrared spectra of the gas and solid have been recorded from 55–2000 cm^?1 . The spectra of the gas have been interpreted in detail on the basis of C_2v symmetry with the A₁ skeletal Si-O-Si bend assigned at 63 cm^?1. The spectra gave evidence that there are structural changes upon condensation of the gas and the Si-O-Si angle approaches linearity in the solid state. The opening of this angle is probably due to crystal packing factors.     

Dipole moment derivatives for SO2

Dipole moment derivatives for the vibration-rotation fundamentals v₁, v₂, and v₃ of ³²S¹⁶O₂ have been computed to have the mean absolute values 60.5, 63.6, and 165.9 esu G^?1/2, respectively. These results include remeasured band intensities for v₁ and v₂.     

Experimental determination of the dissociation energies D0 and De of H2O…HF

The zero-point and equilibrium dissociation energies of the hydrogen-bonded dimer H₂O…HF have been determined as D₀ = 34.3(3) kJmol⁻¹ and D_e = 42.9 (8) kJmol⁻¹ from absolute intensities of rotational transitions in an equilibrium mixture of H₂O, HF and H₂O…HF.     

Measurements of transition probabilities for two N I infrared transitions and their application for diagnostics of low temperature plasmas

Spectra emitted from a wall-stabilized arc, running in a gas mixture of helium, argon, nitrogen, oxygen and traces of hydrogen have been studied. Intensities of selected spectral transitions of neutral nitrogen and oxygen have been measured. Applying the Boltzmann plot method and using a reliable set of O I transition probabilities of spectral lines, originating from levels considerably spread in excitation energies, the temperatures of arc plasmas have been determined. Line intensities of two N I infrared transitions, originating from doubly excited terms 3p′ ²F^o and 3p′ ²G have been measured. In order to obtain the corresponding transition probabilities (A_ki) for these lines, intensities of other N I infrared lines, with well known transition probabilities (taken from recently published data by Wiese and Fuhr [W.L. Wiese and J.R. Fuhr, Improved critical compilations of selected atomic transition probabilities for neutral and singly ionized carbon and nitrogen, J. Phys. Chem. Ref. Data 36 (2007) 1287–1345] from National Institute of Standards and Technology — NIST) have been measured. For evaluation of the transition probabilities the temperatures obtained from the above mentioned O I Boltzmann plots have been used. The results agree satisfactorily with older data found in literature. The new A_ki values for transitions involving the doubly excited levels, together with A_ki values taken from the above mentioned NIST source (used for determination of the new A_ki values), are proposed as a convenient set for determining temperatures of plasmas containing nitrogen atoms.     

Infrared intensities as a quantitative measure of intramolecular interactions XXXVIII [1]. Selenophenes

The infrared intensities of the three ring stretching modes; v₅, v₆ and v₁₅ of a series of 2- and 3-substituted selenophenes have been measured. Using a previously developed valence bond approach these intensities are rationalised in terms of the σ⁰_R constants of the substituent groups.     

Spectra and structure of organophosphorus compounds: XVII. Infrared and Raman spectra. vibrational assignment and barriers to internal rotation for t-butylphosphine

The infrared spectra of gaseous and solid tertiary-butylphosphine, [(CH₃)₃CPH₂], have been recorded from 50 cm^?1 to 3500 cm^?1. The Raman spectra of gaseous, liquid and solid (CH₃)₃CPH₂ have been recorded from 10 to 3500 cm^?1. A vibrational assignment of the 42 normal modes has been made. A harmonic approximation of the methyl torsional barrier from observed transitions in the solid state gave a result of 4.22 kcal mol^?1 and 3.81 kcal mol^?1 in the gaseous state. Hot band transitions for the phosphino torsional mode have been observed. The potential function for internal rotation about the C-P bond has been calculated. The two potential constants were determined to be: V₃ = 2.79 ± 0.01 kcal mol^?1 and V₆ = 0.07 ± 0.01 kcal mol^?1.     

Vibrational spectrum and conformation of cyclopropyldichloroborane

The infrared (3500-40 cm^?1) and Raman spectra (3200-0 cm^?1) have been recorded for cyclopropyldichloroborane in both the gaseous and solid states. Additionally, the Raman spectrum of the liquid was recorded and qualitative depolarization values obtained. Only one conformation has been found in all three physical states and, on the basis of the polarized nature of the Raman band assigned as the BCl₂ antisymmetric stretch, this conformer has been identified as being the bisected structure with C_s molecular symmetry. A complete vibrational assignment is proposed based on Raman depolarization data, infrared gas phase band contours, and group frequencies. These results are compared with the corresponding data in other organoboranes.     

Infrared study of the hydrogen bonding site in a poly-functional schiff base: N(sp2) or N(sp)?

The hydrogen bond complexes between phenol derivatives and the Schiff base [(diphenylmethylene)amino]-acetonitrile have been studied by infrared spectroscopy in carbon tetrachloride solution. The thermodynamic data and the infrared spectra investigated in the ν_OH, ν_CN and ν_CN region indicate that complex formation occurs at the nitrogen atom of the nitrile function. The hydrogen bonding site is in this case governed by the accessibility of the lone pair which is markedly higher for the N(sp) than the N(sp²) electrons.     

Circular dichroism spectra of trans-chalcone epoxides

The electronic absorption and CD spectra of (−)-trans-chalcone epoxide and its derivatives with methyl and alkoxy substituents at the ortho-positions of the aromatic rings have been measured. The spectra have been assigned with help of the energies, oscillatory strengths, and rotatory strengths of the singlet transitions obtained from DFT calculations. The features of the CD spectra, indicative of the absolute configuration, are the carbonyl n–π¹ band and two further strong bands assigned to the overlapping signals of π–π¹ and n_epoxy–π¹ excitations.     

Resolution of cycloplatinated ferrocenylketimines

The resolution of cycloplatinated ferrocenylketimines was carried out by using S-leucine as chiral auxiliary and a pair of diastereomers was obtained. The optically active derivatives of the cycloplatinated ferrocenylketimines have been prepared and characterized. The structures and absolute configurations of (−)-(S_p,S)-[Pt{(η⁵-C₅H₃CMeNC₆H₄-4-CH₃)Fe(η⁵-C₅H₅)}(S-leu)] and (−)-(S_p)-[Pt{(η⁵-C₅H₃CMeNC₆H₄-4-Br)Fe(η⁵-C₅H₅)}(PPh₃)Cl] were determined by X-ray diffraction, on the basis of which the absolute configurations of other optically active compounds studied were ascertained.     

Vibrational energy transfer in CH3I

Previous works have reported vibration—vibration and vibration—translation transfer rates in the methyl halides. Using the technique of laser induced infrared fluorescence we have studied energy transfer in the concluding member of this series, CH₃I. Following excitation by resonant lines of a Q-switch CO₂ laser, infrared fluorescence has been observed from the v₂, v₅ as well as the 2v₅, v₁, v₄ vibrational energy levels of CH₃I. All the observed states exhibit a single exponential decay rate of 23 ± 2 ms^?1 torr^?1. Measurements have also been made on deactivation of the various modes by rare gases. The risetime of the v₂, v₅ levels was found to be approximately 101 ± 20 ms^?1 torr^?1, while that of the 2v₅, v₁, v₄ levels was approximately 225 ± 45 ms^?1 torr^?1. Fluorescence was not detected from the v₃ level. These results are discussed in terms of SSH type theoretical calculations, and comparison is made with the results obtained for other members of the methyl halide series, namely CH₃F, CH₃Cl and CH₃Br.