Electronic states and barriers to internal rotation in silaallenes

The electronic states and barriers to internal rotation in allene ( 1a ), 1-silaallene ( 2a ), and 2-silaallene ( 3a ) are investigated computationally using ab-initio molecular orbital methods. Planar geometries with two-, three-, and four-π-electron configurations have been considered as possible transition states ( 1b–3d ). Structures have been optimized at the Hartree–Fock level with a small split valence basis set (3-21G) and higher level calculations with basis sets of split valence (6-31G ) and split valence plus polarization function (6-31G *) quality include correlation energy estimates from Møller–Plesset second-and third-order perturbation theory. The electronic barrier to internal rotation in allene is estimated near 53 kcal/mol whereas the corresponding barriers in 1-silaallene and 2-silaallene are considerably smaller, ca. 35 and 20 kcal/mol, respectively. The transition states are predicted to possess bent geometries in all three molecules with open-shell singlet, three-π-electron configurations in 1 and 2 ( 1c, 2c ) but a closed-shell singlet, two-π-electron configuration in 3 (3d) .     

Conformations,vibrational spectra and force field of 1-methyl-2-(2′-pyridyl)benzimidazole: experimental data and density functional theory investigation in comparison with 2-(2′-pyridyl)benzimidazole

The molecular structure, conformational equilibria, vibrational spectra and molecular force field of 1-methyl-2-(2′-pyridyl)benzimidazole have been determined at the HF, MP2 and DFT/(B3LYP, BVP86) levels with 6-31+G(d,p) and TZVP basis sets. The torsional potentials for the rotation around the C1–C2 pivotal bond have been calculated at the B3LYP/6-31+G(d,p) and BVP86/TZVP levels of theory for gaseous and aqueous 1-methyl-2-(2′-pyridyl)benzimidazole. FT-Raman (3500–10 cm^?1) and FT-IR (3900–400 cm^?1) spectra of solid 1-methyl-2-(2′-pyridyl)benzimidazole have been recorded and interpreted on a base of calculated potential energy distribution. The results of the experimental and theoretical study of vibrational spectra and molecular structure of 1-methyl 2-(2′-pyridyl)benzimidazole are considered in comparison with similar data for 2-(2′-pyridyl)benzimidazole.

     

Methyl group internal rotation A–E line splittings in several torsionally excited states of methyl glycolate and 2-methoxyethanol

The rotational spectra of several torsional satellites of methyl glycolate and 2-methoxyethanol have been investigated.The methyl barrier to internal rotation in methyl glycolate increases with the torsional quantum number of the C-C skeletal torsion, for which A–E line splittings have been measured up to v_SK=3. The V₃ value determined from the A–E line splittings in the first excited state of the methyl internal rotation is nearly the same of that previously determined in the ground state.For 2-methoxyethanol the V₃ barrier as determined from the A–E line splittings in the ground state is about 20% lower than the value previously obtained from the splittings observed in the first excited state of the methyl internal rotation. The sequence of the A–E splittings in the first excited state of the O-C skeletal torsion (v_SK=1) is probably reversed with respect to the ground state, while in the v_SK=2 state the sequence is like that in the ground state.     

Internal rotation in mononitro-n-alkyl radicals

Internal rotation in the C·H₂(CH₂) _n NO₂ (n ≤ 7) type radicals has been studied. 44 potential functions of the internal rotation, V(φ), have been calculated taking advantage of the B3LYP/6-311++(3df,3pd) and MP2/6-311++(3df,3pd) methods. The trends observed in the series of parameters characterizing the internal rotation have been explained in view of the electron clouds conjugation, the inductive effect of the end groups, the gauche effect, and the rotation tops interaction. The coefficients of V(φ) have been shown to depend predominantly on the nearest surrounding of the rotation axis. Based on this, the generalized functions, V _av(φ), have been developed, their coefficients being dependent exclusively on the rotating bond position. Such functions are convenient for molecular modeling applications.     

Methyl rotation in polydimethylsiloxane studied by neutron transmission

Neutron transmission of polydimethylsiloxane has been measured as a function of neutron wavelength in the range 4–10 Å, at room temperature. Scattering cross sections per hydrogen atom have been obtained and the slope (12.2 ± 0.2) barns/Å has been derived. Comparison with calibration curves relating the slope to the barrier hindering internal rotation as well as comparison with calculated neutron cross sections using the Krieger–Nelkin formalism for different dynamical situations indicates practically free rotation of CH₃ groups about their C₃ symmetry axes.     

Theoretical studies on the rotamers and dynamic behaviors of ethyl-5-acetyl-4-(3′,4′-dimethoxyphenyl)-2,6-dimethyl-1,4-dihydropyridine-3-carboxylate

The potential energy surfaces of ethyl-5-acetyl-4-(3′,4′-dimethoxyphenyl)-2,6-dimethyl-1,4-dihydropyridine-3-carboxylate have been explored by density functional theory B3LYP with 6-31G* basis set method. All minima and maxima points have a flat boat conformation and the aryl ring lies above the 1,4-dihydropyridine ring. Therefore, the rotation of aryl, acetyl, and carboethoxy groups do not cause a major conformational change in this compound. However, the orientations of carbonyl groups and the distortion from planarity of dihydropyridine ring have been changed. Intramolecular H-contacts involving CH-groups as proton donors have also been investigated. Comparative analysis of the results indicates that the barrier to rotation for aryl group is smaller than that of the carbonyl groups. In addition, the barriers to rotation for the carbonyl and aryl groups of the corresponding pyridine, i.e., ethyl-5-acetyl-4-(3′,4′-dimethoxyphenyl)-2,6-dimethyl-pyridine-3-carboxylate, have also been computed by a similar basis set to investigate the effect of aromaticity of the dihydropyridine ring on the these parameters.     

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.     

NMR study of some derivatives of dithiocarbazic acids

The NMR spectra of a series of methyl and phenyl derivatives of dithiocarbazic acid have been examined. The value of the chemical shift of the S-Me group is found to be 2·3–2·6 ppm, while for N²-Me and N³-Meδ is in the range 3·4–3·6 ppm, and 2·4–2·7 ppm, respectively.Present data suggest that the rotation about the SCN and SCS bonds is sterically hindered.     

Studies of magnetic resonance phenomena in polymers. II. Molecular motions in poly(methyl methacrylate) as studied by spin-probe and spin-label methods

Thin films of spin-probed and spin-labeled poly(methyl methacrylate) (PMMA) have been examined by electron spin resonance (ESR) in the temperature range of 77–520°K. The rotational correlation times of nitroxides used as spin probes and labels have been determined as a function of temperature from which activation energies are also determined. The nitroxide rotational times are found to strongly correlate with local segmental and side-chain motions of the host PMMA matrix. Five discrete molecular motions are detected in PMMA along with their activation energies as measured: side-chain CH₃ rotation (1 Kcal/mol), main-chain CH₃ rotation (2 Kcal/mol), ester side-chain COOCH₃ rotation around the C? C bond (4 Kcal/mol), main-chain C? C bond rotation (6 Kcal/mol), and side-chain OCH₃ rotation around the C? O bond (18 Kcal/mol). The activation energies determined by ESR are consistent with the potential-energy barriers calculated theoretically for various rotations in PMMA. It is concluded that the probe and label rotational motions do respond to localized, small-scale segmental and side-chain motions of host polymers but are relatively ineffective in response to the large-scale segmental motion with an activation energy larger than 20 Kcal/mol in the case of PMMA.     

NMR studies of conformations and dynamic processes—1 : [24]cyclophanes with ethylene bridges

The conformations and dynamic processes in a series of relatively unstrained [2₄]paracyclophanes (with one, two or four -CH₂-CH₂-bridges) and some closely related compounds have been analysed. Their ¹NMR spectra have been recorded at low temperatures and the temperature dependence rationalised as being due to essentially two types of dynamic process-the torsional motion around the sp³-sp³ C-C bonds in the bridges, and the rotation around the sp²-sp³ C-C bonds adjacent to the benzene rings. The barriers to the former process are similar for the series of cyclophanes 1–6 and are due to steric and electronic interactions in the syn-oriented transition states. In cyclophanes 7–9, in which anti-orientations of the aromatic rings are possible, the barriers are lower. The latter process, involving the rotation of the benzene rings, becomes important at temperatures below 150 K and has not been further analysed.     

New Saponins from Phytolacca dodecandra l'HERIT

Three bidesmosidic saponins ( 1–3 ) have been isolated from the methanolic extract of the berries of Phytolacca dodecandra l'HERIT (Phytolaccaceae) by a combination of rotation locular counter-current chromatography and column chromatography on reversed phase (RP-8) With MeOH/H₂O. The structures have been established by ¹H-NMR, ¹³C-NMR, FAB-MS, and D/CI-MS, as well as on the basis of acidic and basic hydrolyses. The monodesmosidic saponins 1a–3a obtained after partial hydrolysis with a base exhibit strong molluscicidal activity against the schistosomiasis-transmitting snail Biomphalaria glabrata. Saponins 1–3, 1a , and 3a are reported for the first time, whereas 2a has been identified previously in the aqueous extract of P. dodecandra berries.     

Crystallographic analysis of a pair of isolable atropisomers of 2-aryl substituted indoline derivatives

The crystal and molecular structures of isomeric compounds of 1-(4′-chlorobenzoyl)-2-(2″-hydroxynaphthyl)-3,3-Dimethylindoline have been determined by single crystal X-ray analyses as a pair of diastereomeric atropisomers due to restricted rotation about a Csp³-Csp² bond.     

Effect of fluorinated nematic mesogens on phase behaviors and optical properties of chiral liquid crystalline polysiloxanes

A series of new chiral side-chain liquid crystalline polymers (P₁–P₇) have been synthesized with poly(methylhydrogeno)siloxane, two chiral liquid crystalline monomers, cholesteryl-4-allyloxybenzoate (M₁) and cholesteryl 4-(10-undecylen-1-yloxy) benzoate (M₂), and a nematic liquid crystalline monomer, 4-(trifluoromethyl)phenyl 4-(undec-10-enoyloxy)benzoate (M₃). The chemical structures and liquid crystalline properties of the synthesized polymers have been investigated by FTIR, ¹H-NMR, differential scanning calorimetry (DSC), polarizing optical microscopy (POM), thermogravimetric analysis (TGA), and X-ray diffraction (XRD). All chiral polymers show wide mesophase temperature ranges and a high thermal stability with decomposition temperatures (T _d) at 5 % weight loss greater than 300 °C. P₁–P₄ display a single cholesteric phase, but P₅–P₇ containing more fluorinated units show a smectic A (SA) phase besides a cholesteric phase. The optical properties of the polymers have been characterized by circular polarization spectra and optical rotation analysis. The cholesteric polymers P₃ and P₄ exhibit different colors at room temperature, and the color can remain over 24 months. The maximum reflection bands of polymers P₁–P₄ shift to long wavelength with increasing the content of M₃ in the polymer systems. For P₅–P₇, the reflection wavelengths change sharply around the temperature of the SA–Ch phase transition. The specific rotation value of P₂ smoothly decreases from ?8.2° to ?0.29° when it is heated, but the specific rotation value of polymer P₇ changes from negative value to positive value on heating cycle. The optical properties of the polymers offer tremendous potential for various optical applications.     

Proton magnetic resonance in Sr(NH3)6: Evidence for rapid ammonia diffusion

The proton magnetic resonance linewidth in Sr(NH₃)₆ has been measured in the range 40–300 K. Two line-narrowing transitions have been detected as the temperature is increased. Between 40 and 54 K the linewidth decreases from about 2 to 1.6 G, and in the range 97–140 K the line narrows from about 1.6 G to 15 mG. The results are interpreted in terms of proton tunneling at low temperatures, a transition from tunneling to classical rotation of ammonia molecules between 40 and 54 K, and an ammonia diffusional transition with an activation energy of about 3 kcal/mole in the range 97–140 K.     

A comparison of the structure,flexibility and mesogenic properties of 4-methoxy-4′-cyanobiphenyl and the α,α,α-trifluorinated derivative

Abstract

The compound 4-cyano-4′-(α,α,α-trifluoromethoxy)biphenyl (1OCBF₃) has been synthesized. Unlike the fully protonated analogue, 4-cyano-4′-methoxybiphenyl (1OCB), it does not show a liquid crystalline phase on cooling from the melting point (51°C) to room temperature. The transition temperature to a monotropic nematic phase was obtained as approximately 0°C by determining the transition temperatures of mixtures with 1OCB. The structures, conformational properties and orientational ordering of both 1OCB and 1OCBF₃ as solutes in a nematic solvent ZLI 1132 have been investigated via the 17 dipolar couplings obtained by analysing the proton and fluorine NMR spectra of these solutions. It is concluded that the major difference between the two molecules lies in the potential, V(φ₂), governing rotation about the ring–oxygen bonds. In 1OCB the potential has the same form as in anisole, with a minimum when the C–O bond is in the plane of the attached ring (φ₂ = 0°), and a maximum of about 15 kJ mol^?1 when φ₂ is 90°. In 1OCBF₃ the barrier to rotation about the ring–O bond decreases substantially to being near zero.     

Isomerization barriers in bis(4H-thiopyran) and in bithioxanthenes

The inversion and rotation mechanisms for the isomerization of Feringa’s bithioxanthenes existing in two conformations, up/up and up/down, have been calculated at the B3LYP/6-31G(d) and B3LYP/6-311++G(d,p) levels. The inversion mechanism that maintains the double bond nature of the central bond is a classical one but the rotation mechanisms that break the double bond to form a biradical needs to explore the singlet and triplet states. To do this we have removed the four fused phenyl rings of bithioxanthene and calculated at the CASSCF and CASPT2 levels bis(4H-thiopyran) proving that B3LYP calculations yield reasonable results for the rotation barriers.     

Calculation of the tau dependence of the vibration-internal rotation-overall rotation interactions in CH3OH from molecular structure and molecular dynamics

The Guan and Quade theory for vibration-large-amplitude internal-motion-rotation interactions has been applied to the internal rotation problem in CH(3)OH. Through the molecular dynamics, the cos 3tau and sin 3tau dependence of the torsional-rotational coefficients in the effective Hamiltonian have been calculated from molecular structure. The internal rotation coordinate tau(') for the vibrationally distorted molecule is shown to have the necessary threefold symmetry for all values of tau('). For the methyl deformation modes, the vibrational dependence of the internal rotation potential energy is shown to have a threefold symmetry. The S(t) and S(t)S(t) dependence of the inertia tensor and Coriolis coupling coefficients has been developed in terms of curvilinear internal coordinates. The T transformation separating rotation from vibrations in zeroth order is then applied, the kinetic-energy tensor inverted to momentum space, and finally the effective torsion-rotation coefficients are calculated by Van Vleck perturbation theory. When compared to the empirical results, the kinetic-energy contributions to the cos 3tau and sin 3tau dependence of the coefficients are as follows: 54% of P(a)(2) is accounted for, 28% of P(a)P(b), 16% of P(a)P(c), and 91% of the asymmetry. The calculation is inadequate to account for the P(b)(2),P(c)(2), and P(b)P(c) coefficients, ranging from factors of 20-70, even with the incorrect sign for some of the terms. Anharmonic force contributions from the vibrations have not been used in the calculation since these forces are not known at this time.     

Cooperative effects in restricted rotations of aryl groups in 2,4,6,8-tetraary-3,7-diazabicyclo[3.3.1]nonanes and related systems

The free energies, enthalpies and entropies of activation for the rotation of the aryl groups in the N,N′-dimethyl and N,N′-dichloro derivatives of rel-(2R,4S,6S,8R)-2,4,6,8-tetrakisaryl-3,7-diazabicyclo[3.3.1]nonanes have been determined and compared with related tricyclic systems which cannot undergo chair-to-boat conformational changes. It is concluded on the basis of the large, negative value of ΔS³ for rotation of the 2(4) aryl group that this rotational process is correlated with rotation of the 8(6) aryl group. The 8(6) aryl group can however rotate independently of the 2(4)-aryl group. The usefulness of the entropies of activation as a criterion for cooperative rotation of groups is briefly discussed.     

Molecular structure and internal rotation potential of perfluoro (2,4-dimethyl-3-oxa-2,4-diazapentane), (CF3)2N–O–N(CF3)2

Ab initio quantum chemical calculation were performed on R₂N–O–NR₂ type (R=H, F, CH₃ and CF₃) molecules, using the HF, B3LYP and MP2/6-31G* levels of theory. The equilibrium structures and the internal rotation potentials have been determined. Three stable conformers were found for R=H, F and CH₃ while only two in case of R=CF₃. The rotation potential energy curves do not change significantly upon fluorination. The calculations suggests that in the ED measurement of the title compound the NC and NO bond length might have been interchanged.