The structure analysis of triaryl derivatives of the group V elements: V. Spectra,crystal and molecular structure of trimesitylarsine,C27H33As

The complete X-ray structure analysis of trimesitylarsine (TMAS), C₂₇H₃₃As, has been performed. The crystals are triclinic, a 18.718, b 16.418, c 8.204 Å, α 99.99, β 97.85, γ 104.56°, Z = 4, space group P1̄ (two independent molecules in the asymmetric unit); the final value of the R-factor is 0.038. In the electronic spectrum of TMAS the long-wave band has the maximum at 276 nm which differs significantly from that of triphenylarsine (TPAS) at 249 nm. The bathochromic spectral shift and the molecular conformation are caused by the steric effects as a result of bulky methyl groups in the positions 2,4 and 6 in the phenyl rings. Two independent molecules are connected by a pseudo-axis of symmetry.     

NMR spectra of oriented 2,2,2-trifluoroethanol (CF3CH2OH)

Photolysis of hydrogen sulphide in argon, nitrogen and carbon monoxide matrices at 20 K produces HS radicals and S atoms. On warming the matrix, H₂S₂ and S₂ molecules are formed as a result of recombination reactions. The latter are identified by a blue-purple emission observed during warm-up of the matrix.     

An electron-diffraction study of the molecular structure of gaseous perbromyl fluoride and calculation of its force field and vibrational amplitudes

The molecular structure of FBrO₃ has been studied by gas-phase electron diffraction. Least-squares refinements of the molecular geometry using fixed spectroscopic amplitudes revealed two geometrical minima. Initially, the amplitudes employed were derived from diagonal force fields obtained by spectroscopic least-squares refinements to fit observed and calculated wave numbers; for each geometry there are two spectroscopic minima. In the lowest geometrical minimum the wave number agreement is poor, however, the introduction of the ∠OBrO/∠FBrO interaction force constant removed the discrepancies; the resulting force field is F(Br-O) = 6.92 ± 0.02 mdyn Å^?1F(Br-F) = 3.22 ± 0.03 mdyn Å^?1, F(∠OBrO) = 1.06 ± 0.02 mdyn Å, F(∠FBrO) = 0.81 ± 0.03 mdyn Å, F(∠OBrO/∠FBrO) = ?0.19 ± 0.02 mdyn Å. In the corresponding geometrical minimum r_g(Br-O) = 1.582 ± 0.001 Å, r_g(Br-F) = 1.708 ± 0.003 Å, r_α(∠OBrO) = 114.9 ± 0.3°, r_α(∠FBrO) = 103.3 ± 0.3°. Perpendicular amplitude correction coefficients, calculated for each force field employed, were used throughout to relate the interatomic distances through the r_α-structure. The geometries of the r_α^o- and r_e-structures are estimated.     

Ab initio calculation of the dipole moment function of hydrogen iodide

SCEP/CEPA and MC SCF potential energy and dipole moment functions for hydrogen iodide have been calculated. Spectroscopic constants and vibrational dipole matrix elements obtained from the CEPA functions are in good agreement with experimental data. In contrast to previous results for hydrogen fluoride, the MC SCF dipole moment function is less accurate than the CEPA function.     

The molecular structure and conformation of gaseous bis(chloromethyl)dimethyl silane as determined by electron diffraction

The molecular structure of bis(chloromethyl) dimethyl silane has been investigated in the gas phase at a nozzle temperature of 60° C. The molecules exist mainly in the GG form with the presence of 30% (+10%, ?20%) AG form. The values of the principal distances (r_a) and angles with estimated error limits of 2σ are r(C-H) = 1.093 (0.009) Å, r(C-Cl) = 1.801 (0.019) Å, r(Si-C) (the average Si-C bond) = 1.875 (0.009) Å, ∠(CSiC) = 109.5°, ∠(SiCCl) = 110.5° (0.4), ∠(CCH) = 112.5° (1.8) and φ (the gauche torsion angle relative to 0° for the anti form) = 117.4° (3.8).     

The molecular structure of gaseous tetrachloro-p-benzoquinone and tetrachloro-o-benzoquinone by electron diffraction

The structures of tetrachloro-p-benzoquinone and tetrachloro-o-benzoquinone (p- and o-chloranil) have been investigated by gas electron diffraction. The ring distances are slightly larger and the carbonyl bonds slightly smaller than in the corresponding unsubstituted quinones. The molecules are planar to within experimental error, but small deviations from planarity such as those found for the para compound in the crystal are completely compatible with the data. Values for the geometrical parameters (r_a distances and bond angles) and for some of the more important amplitudes (l) with parenthesized uncertainties of 2σ including estimated systematic error and correlation effects are as follows. Tetrachloro-p-benzoquinone: D_2h symmetry (assumed); r(CO) = 1.216 Å(4), r(CC) = 1.353 Å(6), r(C-C) = 1.492 Å(3), r(C-Cl) = 1.701 Å(3), ∠C-C-C = 117.1° (7), ∠CC-C1 = 122.7° (2), l(CO)= 0.037 Å(5), l(CC) = l(C-C) - 0.008 Å(assumed) = 0.049 Å(7), and l(C-Cl) = 0.054 Å(3). Tetrachloro-o-benzoquinone: C_2v symmetry (assumed); r(CO) = 1.205 Å(5), r(CC) = 1.354 Å(9), r(C_cl-C_cl) = 1.478 Å(28), r(Co-C_cl) = 1.483 Å(24), r(C_o-C_o) = 1.526 Å(2), r(C-Cl)= 1.705 Å(3), <C_o-CO = 121.0° (22), ∠C-C-C = 117.2° (9), ∠C_co, ClC-Cl = 118.9° (22), ∠C_ccl, ClC-Cl = 122.2°(12), l(CO) = 0.039 Å(5), and l(C_cl-C_cl) = l(C_o-C_cl) = l( Co-Co) = l(CC) + 0.060 Å(equalities assumed) = 0.055 Å(9). Vibrational'shortenings (shrinkages) of a few of the long non-bond distances have also been measured.     

An electron diffraction investigation of the molecular structure of dichloromaleic anhydride

The molecular structure of gaseous dichloromaleic anhydride has been investigated by electron diffraction at a nozzle-tip temperature of 164–170°C. The molecule is planar to within experimental error, but small deviations from planarity corresponding to torsion up to about 10° around the carbon-carbon single bonds cannot be ruled out. Values of the more important r_α distances and angles with estimated 2σ uncertainties are r(CO) = 1.188(2) Å, r(CC) = 1.332(5) Å, r(C-O) = 1.389(3) Å, r(C—C) = 1.495(3) Å, r(C—Cl) = 1.685(2) Å, ∠CC-Cl = 129.4(2)°, ∠C-CO = 128.5(4)° and ∠CC—C = 107.9(2)°. The shortening of the carbonyl bond relative to that in maleic anhydride itself is discussed in terms of a possible general effect of vicinal substitution.     

On the barrier to internal rotation in trichloromethyl trichlorogermane,Cl3CGeCl3

Consideration of the continuing successes of the theory of condensed phase isotope effects in the harmonic approximation leads to the conclusion that relative changes expected in anharmonic constants on condensation are constrained to be of the same order of magnitude or smaller than the corresponding changes in harmonic force constants. Benzene-deuterobenzene isotope efforts are analyzed in an illustrative example and a brief discussion of other cases, including CS₂ and CHCl₃, is given.     

Molecular structure and conformation of gaseous chloroacetyl chloride as determined by electron diffraction

Chloroacetyl chloride is studied by gas-phase electron diffraction at nozzle-tip tempera- tures of 18, 110 and 215°C. The molecules exist as a mixture of anti and gauche confor- mers with the anti form the more stable. The composition (mole fraction) of the vapor with uncertainties estimated at 2σ is found to be 0.770 (0.070), 0.673 (0.086) and 0.572 (0.086) at 18, 110 and 215°C, respectively. These values correspond to an energy difference with estimated standard deviation ΔE^o = E^o_g -E^o_a = 1.3 ± 0.4 kcal mol^?1 and an entropy difference ΔS^o = S^o_g -S^o_a = 0.7 ± 1.1 cal mol^?1 K^?1. Certain of the diffraction results permit the evaluation of an approximate torsional potential function of the form 2V = V₁(1 - cos φ) + V₂(1 - cos 2φ) + V₃(1 - cos 3φ); the results are V₁ = 1.19 ± 0.33, V₂ = 0.56 ± 0.20 and V₃ = 0.94 ± 0.12, all in kcal mol^?1. The results for the distance (r_a), angle (_∠α) and r.m.s. amplitude parameters obtained at the three temperatures are entirely consistent. At 18°C the more important parameters are, with estimated uncertainties of 2σ, r(C-H) = 1.062(0.030) Å, r(CO) = 1.182(0.004) Å, r(C-C) = 1.521(0.009) Å. r(CO-Cl) = 1.772(0.016) Å, r(CH₂-Cl) = 1.782(0.018) Å, ∠C-C-0 = 126.9(0.9)°, ∠CH₂-CO-C1 = 110.0(0.7)°,∠CO-CH₂-C1 = 112.9(1–7)°, ∠H-C-H = 109.5° (assumed), ∠φ (gauche torsion angle relative to 0° for the anti form) = 116.4(7.7)°, δ (r.m.s. amplitude of torsional vibration in the anti conformer) == 17.5(4.2)°.     

A square-wave wavelength modulation system for automatic background correction in carbon furnace atomic emission spectrometry

A square-wave wavelength modulation system, based on a rotating quartz chopper with four quadrants of different thicknesses, has been developed and evaluated as a method for automatic background correction in carbon furnace atomic emission spectrometry. Accurate background correction is achieved for the residual black body radiation (Rayleigh scatter) from the tube wall and Mie scatter from particles generated by a sample matrix and formed by condensation of atoms in the optical path. Intensity modulation caused by overlap at the edges of the quartz plates and by the divergence of the optical beam at the position of the modulation chopper has been investigated and is likely to be small.     

Equilibrium and calorimetric study of the hydration of anion-exchange resins

The adsorption of water vapour on anion-exchangers of various degrees of cross-linking ( x 2, x 4, x 8, x 10) and in different ionic forms (Cl(-), Br(-), I(-)) was studied by the isopiestic technique. The calculated integral free-energy changes were independent of the degree of cross-linking of the resins. With increase in the number of adsorbed water molecules the free-energy functions approached limiting values which were characteristic for the counter-ions. The free-energy change was combined with the enthalpy of water sorption (obtained from direct calorimetric measurements) to obtain the entropy change due to the water uptake. Both the enthalpy and the entropy functions indicated the existence of several processes during the adsorption of water, among which the most relevant are hydration, swelling of the matrix, and dilution of the internal electrolyte of the ion-exchanger.     

Some considerations of the steady-state and transient behaviour of membrane-covered dissolved oxygen detectors

The behaviour of commercial, membrane-covered dissolved oxygen detectors is considerably more complicated than the orginal model of Mancy et al. would suggest. For example, the steady-state current is dependent both on the thickness and nature of the electrolyte behind the membrane. And transient currents obtained for switch-on of the detector are not completely described by the simple diffusional model. This paper examines these examples of more complicated behaviour. An analysis of the transient current for a step change in dissolved oxygen concentration is also given.     

Molecular structure and conformation of gaseous bromoacetyl chloride and bromoacetyl bromide as determined by electron diffraction

Bromoacetyl chloride and bromoacetyl bromide are studied by gas phase electron diffraction at nozzle-tip temperatures of 70°C and 77°C, respectively. Both compounds exist as mixtures of anti and gauche conformers. The mole fraction anti, with uncertainties estimated at 2σ, was found to be 0.474(0.080) for bromoacetyl chloride and 0.615(0.069) for bromoacetyl bromide. The results for the distance (r_a)and angle (∠α) parameters, with parenthesized uncertainties of 2σ including estimated uncertainty in the electron wave length and correlation effects are as follows: (1) bromoacetyl chloride, r(C-H) = 1.086(0.062) Å, r(CO) = 1.188(0.009) Å, r(C-C) = 1.519(0.018) Å, r(C-Cl) = 1.789(0.011) Å, r(C-Br) = 1.935(0.012) Å, ∠C-CO = 127.6(1.3)°, ∠C-C-Cl = 111.3(1.1)°, ∠C-C-Br = 111.0(1.5)°, ∠H-C-H = 109.5°(assumed), $\text{}\text{?}$/o (gauche torsion angle relative to 0° for the anti form) = 110.0°(assumed); (2) bromoacetyl bromide, r(C-H) =1.110(0.088) Å, r(C=O) = 1.175(0.013) Å, r(C-C) = 1.513(0.020) Å, r(CO-Br) = 1.987(0.020) Å, r(CH₂-Br) = 1.915(0.020) Å, ∠C-CO = 129.4(1.7)°, ∠CH₂-CO-Br = 110.7(1.5)°, ∠CO-CH₂-Br = 111.7(1.8)°, ∠H-C-H = 109.5°(assumed), ∠ø (gauche torsion angle relative to 0° for the anti form) = 105.0°(assumed). The structural results are discussed in connection with the structures of related molecules.     

Molecular structure of F2POPF2: an electron diffraction study

The most important geometric parameters and associated uncertainties (2σ) determined for F₂POPF₂ are the distances (r_g) P-O = 1.631 ± 0.010 Å, P-F = 1.568 ± 0.004 Å, and angles POP = 135.2 ± 1.8°, OPF = 97.6 ± 1.2°, and FPF = 99.2 ± 2.4°. Amplitudes of vibration were also found. The large POP angle and relatively short P-O bond length are consistent with a significant degree of pπ-dπ bonding. Our structure interpretation differs from an earlier one reported by Arnold and Rankin in the relative P-O and P-F bond lengths and in the conclusion that the molecule exists in a distribution of not very rigid, probably staggered, conformers instead of one fairly rigid structure.     

Methyl group rotation barrier in γ-picoline

Ab initio calculations on γ-picoline predict a small methyl rotational barrier of approximately 14 calories mole^?1 in good agreement with the experimental value of 13.7 calories mole^?1 [1].     

Trends in the CNDO/2 molecular orbital study of electronic structure in some neurotransmitter drugs

An investigation of electronic structure in some neurotransmitter drugs has been made using the CNDO/2 semi-empirical molecular orbital method.The electronic structure has been conveniently characterized by the electronic parameters nett atomic population (NAP) and bond index (BI). A variation of these electronic parameters with respect to conformation has been studied and has been found unlikely to exceed 0.1 e in most. cases. Further, the useful extent to which the electronic parameters of some commonly occurring functional groups may be regarded as conformationally invariant has been demonstrated. Also presented are (i) a discussion on the intramolecular close-approach of functional groups — the interaction between terminal —COO^? and ?NH₃⁺ groups of α-ω anaino acids is explicitly considered; (ii) an enquiry into the extension of ‘standard’ (idealized) geometry models in the elucidation of electronic structure.The implication of the results and observations presented here are briefly discussed with reference to classical and quantum structure-activity studies of drug molecules.     

Halogenation of 1,1-diarylethylenes by N-halosuccinimides

An efficient method for the preparation of 2,2-diarylvinyl halides from the corresponding 1,1-diarylethylenes has been developed. N-Halosuccinimides (N-bromosuccinimide or N-chlorosuccinimide) were used as the halogenation reagents. The practicability of this method is highlighted by its simple operation, broad substrate scope and capability for large-scale reaction.     

Green synthesis of gold nanoclusters using papaya juice for detection of l-lysine

P-AuNCs was rapidly synthesized, while papaya juice served as a capping and reducing agent. Due to the surface electron density increase-induced fluorescence enhancing principle, the prepared fluorescent probe provided high selectivity and sensitivity for monitoring L-lysine in human urines.     

Infrared dichroism and molecular conformation of crystalline tetramethyldisiloxanediol

Vibrational spectra of tetramethyldisiloxanediol (TMDD) have been studied in solution and also in the solid state. Polarized IR spectra of oriented crystalline films have been recorded in the frequency range 4000–200 cm^?1. The structure of the molecules in solution has been found to be of C_2v symmetry. On the basis of the IR dichroitic data obtained for the oriented crystalline films, the molecules should have no symmetry in crystals (C₁ site symmetry) and the structure of OC₂SiOSiC₂O skeletal fragment may be described with an angle of torsion of about 70° around the (Si)O-Si bond.