Resonant cars spectroscopy of s-tetrazine vapour

CARS experiments on s-tetrazine vapour show that the electronic resonance enhancement in the Q-branch is most effective for the lower J values. This suggests that the radiationless relaxation rate in the excited state increases with rotational quantum number. Delayed picosecond CARS experiments indicate that the rotation-vibration coupling for the 1008 cm^?1 ground-state vibrational mode is approximately 2 MHz.     

Pavoninins,shark-repelling and ichthyotoxic steroid n-acetylglucosaminides from the defense secretion of the sole pardachirus pavoninus (soleidae)

Six steroid itN-acctylglueosaminides, pavoninins-1 to -6, have been isolated from the defense secretion of the sole P. pavoninus guided by ichthyotoxicity and hemolytic activity, and their structures determined to be 1–6 by spcctroscopic studies and chemical correlations. The pavoninins are considered to be the factors responsible for the repellent property of the sole against predatory fishes.     

The crystal structure of bicyclo [3.3.3]undecane-1,5-diol and the conformation of bicyclo[3.3.3]undecane (manxane)

The crystal structure of bicyclo [3.3.3]undecane-1,5-diol has been determined. It is monoclinic, P2₁/c, a = 12.99(2), b = 14.16(2), c = 12.50(1)A,β = 112.42(2)°, with two independent molecules in the asymmetric unit. One of these is disordered, but the other has almost exact C_3h symmetry and its conformation and precise molecular geometry agree well with previous calculations by molecular mechanics. The molecule shows considerable angle strain, having bridge angles in the range 118–121°     

Ion-exchanger ultraviolet spectrophotometry for uranium(VI)

A sensitive method based on solid-phase spectrophotometry has been developed for the microdetermination of uranium(VI) in water samples. Uranium is sorbed on the anion-exchanger QAE-Sephadex from thiocyanate solution and the absorbance of the exchanger is measured at 300 nm. This method is about 30 times more sensitive than solution spectrophotometry. Absorption spectra of various metals in the anion-exchanger phase are presented and their interferences discussed. A procedure for the cation-exchange separation of uranium from accompanying elements before spectral measurement of uranium is proposed.     

The crystal and molecular structure of dl-BI-(o-trimethyl-cis-brazilane)

X-ray crystallographic analysis has established the crystal and molecular structure of the title compound, C₃₈H₃₈O₈. The monoclinic crystals belong to the centrosymmetric space group P2₁/c, with a = 16.701(5), b = 8.037(2), c = 23.600(9) Å, β = 93.10(2)° and Z=4. The structure was solved by direct methods from diffractometer data measured with CuKα radiation, and refined to a final R index of 0.081 for the 2088 observed terms. The dimeric molecule has approximate two-fold symmetry and its presence in the unit cell in both chiralities forms a racemic structure. The three central bonds, C(10)-C(11), C(11)-C'(11), C'(11)-C'(10), are significantly elongated with a mean value 1.59 Å.     

Far-infrared laser magnetic resonance spectrum of SeD (X2Π32)

Far-infrared laser magnetic resonance (LMR) spectra of SeD have been detected at 513 μm using a formic acid laser, and assigned to Zeeman components of the J = $\text{3}\text{2}$ → $\text{5}\text{2}$ transition in the six isotopic forms ^{82,80,78,77,76,74}SeD. Analysis yields the following B_o constants (cm^?1): ⁸²SeD 3.96047, ⁸⁰SeD 3.96284, ⁷⁸SeD 3.96532, ⁷⁷SeD 3.96657, ⁷⁶SeD 3.96793 and ⁷⁴SeD 3.97066. These values, combined with B_o for ⁸⁰SeH from 5.6μm LMR, yield r_e = 0.14634 nm for SeD.     

Sur une nouvelle interaction intramoléculaire attractive influencant les équilibres conformationnels de Σ-4 cyclohexanones

The structural study of cyclohexanones with polar substituants in the γ position

shows:(1) lack of solvent effect on the conformational equilibria, giving a result which differs from those already obtained from α halogeno cyclohexanones(2) the predominance of the axial conformation due to syn diaxial attractive interactions.This work has been done by means of model compounds with a fixed conformation, synthesised by chlorination of corresponding Σ-4 cyclohexanones in α or αα' positions; their structural study gives supplementary proof of the existence of syn diaxial attractive interactions in the studied molecules.     

Synthesis of mevalonolactone (hiochic acid lactone) employing asymmetric epoxidation as the key-step

(R)( — )-Mevalonolactone (hiochic acid lactone)of 91–93%e.e. was synthesized from an achiral starting material employing the Sharpless asymmetric epoxidation as the key-step.     

Methyl group hopping reorientation and the non-existence of spin symmetry species at room temperature

A series of experiments is discussed which, it has been claimed, demonstrate that hindered methyl groups exist at room temperature as relatively long-lived proton spin symmetry species. It is concluded that this concept lacks a theoretical foundation, conflicts with the model of random hopping reorientation between localised states, and leads to physically implausible predictions.     

A thermal lensing study of a photolysis of di-t-butyl peroxide

A photolysis of di-t-butyl peroxide (BOOB) was studied by using a thermal lensing technique. This technique is found to be applicable to the determination Of the rate Constants of the decay of t-butoxy radical (BO ) and the hydrogen abstraction reaction.     

Energy and angular differential cross sections for K + NO2 charge transfer reactions

Doubly differential cross sections, in energy and angle, are reported for the electron transfer reaction between potassium and nitrogen dioxide in a crossed beam apparatus at relative collision energies between 2.7 and 30.8 eV. The formation of NO^?₂ in its ground ¹A₁ and excited ³B₁ state has been observed. Theoretical consideration of these processes indicates that bond bending during the collision has a stronger influence on ion-pair formation than bond stretching. At the lower collision energies most of the excess energy is converted into internal energy of NO^?₂.     

Cationic di- and mono-carbonyl complexes of manganese(I)

The complexes fac-O₃ClOMn(CO)₃(NN) (NN = 1,10-phenantroline (phen) or 2,2'bipyridine (bipy)) react with an excess of the ligands L [L = P(OR)₃ or P(OR)₂Ph, R = Me or Et] in refluxing ethanol to give cis-trans-[Mn(CO)₂-(NN)L₂]ClO₄, or the more highly substituted [Mn(CO)(NN)L₃]ClO₄ if the reaction is carried out under UV irradiation. Carbonylation at normal pressure of the latter complexes results in the formation of cis-cis-[Mn(CO)₂(NN)L₂]ClO₄, which undergo isomerization to the cis-trans isomer when heated in acetone.Treatment of fac-O₃ClOMn(CO)₃(dpe) (dpe = 1,2-bis(diphenylphosphino)-ethane] with bipy or phen in refluxing ethanol gives the corresponding cis-[Mn(CO)₂(NN)(dpe)]ClO₄ complexes, and irradiation of these with UV in the presence of an excess of P(OR)₃ (R = Ph, Et or Me) gives the monocarbonyls [Mn(CO)(NN)(dpe)L]ClO₄.     

The multiphoton ionization spectrum of toluene in a supersonic free jet: internal rotation of the methyl group

The S₁← S_o electronic transitions of toluene involving also some internal rotational levels were observed for the first time in the multiphoton ionization spectrum in a supersonic jet. A large population in several low-lying internal rotational levels and a strong coupling between electronic motion and the internal rotation are suggested.     

A minicomputer program based on additivity rules for the estimation of 13c-nmr chemical shifts

A minicomputer program for the estimation of ¹³C-n.m.r. chemical shifts based on simple additivity rules is described.     

Copper(II)-cetyltrimethylammonium chloride-chromal blue G ternary complex and its application to the spectrophotometric determination of copper(II)

A sensitive spectrophotometric method for the determination of copper(II) based on a ternary complex with chromal blue G, a triphenylmethane reagent in the presence of cetyltrimethylammonium chloride, is described. The sensitivity of color reaction between copper and chromal blue G has been greatly increased by the sensitizing action of cetyltrimethylammonium chloride, a cationic surfactant. The color development of the ternary complex can be utilized in the highly sensitive spectrophotometric determination of copper. The molar absorptivity of the binary complex between copper and chromal blue G ε_630nm = 9.56 × 10³liters · mol⁻¹ · cm⁻¹ is enchanced on ternary complex formation to ε_{542 nm} = 4.78 × 10⁴liters · mol⁻¹ · cm⁻¹. The ternary complex gave a maximal absorbance at 542 nm in the pH range 9.8–11. Beer's law is obeyed up to at least 1.2 ppm of copper. The maximal absorbance of the ternary complex was found to develop within 5 min and then it remains constant for several hours. The formation constant of the ternary complex is calculated to be 8.6 × 10¹⁰ under these conditions.     

Mixed ligand complexes of ruthenium(III), rhodium(III) and iridium(III) with dipicolinic acid and some monobasic bidentate nitrogen,oxygen donor ligands

The trivalent ruthenium, rhodium and iridium complexes of dipicolinic acid and its mixed ligand complexes with several nitrogen, oxygen donor molecules, of types: Na[M(dipic)₂]·2H₂O and [M(dipic)(N-O)]·nH₂O (where M = Ru(III), Rh(III) or Ir(III); dipicH₂ = dipicolinic acid; NOH represents different nitrogen, oxygen donor molecules, viz., picolinic acid, nicotinic acid, isonicotinic acid, glycine, aminophenol, o- or p-aminobenzoic acid), have been synthesized and characterised on the basis of elemental analyses, electrical conductance, magnetic susceptibility measurements and spectral (electronic and infrared) data. The parent dipicolinic acid complexes are found to have a six-coordinate pseudooctahedral structure, whereas for mixed ligand complexes, a polymeric six-coordinate structure has been assigned. Various ligand field and nephelauxetic parameters have also been evaluated.     

Molecular structures of inorganic compounds of low volatility: I. Salts of oxygen acids of the type M2XO4

We report an electron diffraction study of the molecular structure of gaseous cesium and thallium sulphates and cesium molybdate and tungstate. The average structure found for the M₂XO₄ molecules is described by a model (symmetry D_2d) in which the metal atoms bridge two edges of an XO₄ tetrahedron to form two 4-membered mutually perpendicular planar MO₂X rings.The data lead to conclusions on the complex nature of intramolecular motion. This motion may roughly correspond to great displacements of metal atoms on the surface of an imaginary sphere described near the tetrahedral acid residue.     

Crystalline hydrogen bonded adducts of oxygen bases with peroxybenzoic acids

The preparation and isolation of several crystalline 1 : 1 adducts of substituted peroxybenzoic acids with triphenylphosphine oxide, triphenylarsine oxide, and pyridine oxides, is reported. Infrared spectra indicate the presence of strong intermolecular hydrogen bonds in these adducts.     

Reactions of water with carbon and ethylene over illuminated pt/tio2

The room temperature reaction between gas phase water and active carbon to form carbon dioxide and hydrogen on a platinized titanium dioxide catalyst, illuminated with band gap radiation, is reported. Using the same catalyst system, ethylene is converted to ethane, carbon dioxide, hydrogen and a small amount of methane.