Vibrational Spectra and Normal Coordinate Analysis of N-Methyl Thiourea

The infrared spectra of N-methylthiourea (NMTU) and its N-deuterated and S-methylated species were measured. Assignment of the infrared and Raman spectra of NMTU has been accomplished by correlation with thiourea and by use of infrared band shifts on N-deuteration as well as S-methylation. Normal coordinate analysis was performed for all the fundamentals of NMTU and NMTU-d3, the assignments obtained from the force field calculations being discussed in relation to those in other related thioureas and thioamides. The potential barriers to the internal rotations for the �NH2, �CH3, and �CN groups were estimated from the force constants.

Vibrational Spectra and Assignments for the Fundamental Vibrations of Imidazolidine-2-thione and -2-selenone

Infrared spectra of imidazolidine-2-thione (N,N?-ethylenethiourea, ETU) and its N,N?-deuterated (ETU-d2) and S-methylthiouronium iodides have been recorded from 4000 to 30 cm?1. Normal coordinate analyses of ETU and ETU-d2 have been made for all the fundamental frequencies, employing a Urey-Bradley potential function supplemented with valence type constants for the out of plane modes of the planar skeleton. Raman frequencies of ETU from literature have been utilised. The results of the vibrational analyses are discussed in relation to the group frequencies in structurally related molecules and frequency shifts on deuteration and S-methylation. The normal coordinate treatment is also performed for the planar vibrations of imidazolidine-2-selenone (N,N?-ethyleneselenourea, ESU) to propose assignments for ESU and so also to support the assignments of ETU.

Preparation and NMR spectra of four isomeric diformyl2.2]paracyclophanes (cyclophanes 66)

Four isomeric dialdehydes 4, readily available from cycloaddition of propiolic aldehyde (2) to 1,2,4,5-hexatetraene (1), were separated by chromatography and recrystallization, and were characterized by their spectroscopic data. The individual isomers can now be easily identified from their H-1 NMR spectra even if only one of them is present.

Relation between effective atomic charge and chemical shifts in X-ray absorption spectra of transition-metal compounds

Chemical shifts of K absorption discontinuities, Delta E, of several manganese, iron and cobalt oxides with the metal in the formal oxidation states between +2 and +4, have been measured. These data, together with data in the literature on other compounds of these metals, can be fitted into the expression Delta E=aq+bq2, where q is the effective atomic charge on the metal. Theoretical considerations also support this functional relationship between Delta E and q.

Synthesis, infrared spectra and thermoanalytical properties of transition metal sulfite hydrazine hydrates

Transition metal sulfite hydrazine hydrates, MSO3·xN2H4·yH2O whereM=Mn, Fe, Co, Ni and Zn have been prepared and characterized by chemical analysis, infrared spectra, thermoanalytical and combustion studies. The colours,x andy parameters of the complexes varied depending upon the preparation conditions. Thermal decomposition characteristics differ from metal to metal yielding metal oxides at relatively low temperatures.Mittels chemischer Analyse, IR-Spektren, thermoanalytischen und Verbrennungsstudien wurden die Hydrazinhydrate der hergestellten Übergangsmetallsulfite MSO3·xN2H4·yH2O mitM=Mn, Fe, Co, Ni und Zn beschrieben. Farbe sowie die Parameterx undy der Komplexe hängen von den Herstellungsbedingungen ab. Die thermische Zersetzung, bei der bei relativ niedrigen Temperaturen Metalloxide entstehen, ist von Metall zu Metall verschieden.

Determination of the sign of the order parameter from MAS spectra of oriented molecules

The use of the intensities of the spinning sidebands in the magic-angle spinning spectra of oriented molecules is proposed for the determination of the signs of the order parameters. The method is demonstrated for benzene and chloroform oriented in nematic phases of liquid crystals. On the basis of the theoretical expressions derived for the various order sidebands, the applicability of the method for different experimental conditions is discussed.

NDDO-based CI methods for the prediction of electronic spectra and sum-over-states molecular hyperpolarization

NDDO-based (AM1) configuration interaction (CI) calculations have been used to calculate the wavelength and oscillator strengths of electronic absorptions in organic molecules and the results used in a sum-over-states treatment to calculate second-order-hyperpolarizabilities. The results for both spectra and hyperpolarizabilities are of acceptable quality as long as a suitable CI-expansion is used. We have found that using an active space of eight electrons in eight orbitals and including all single and pair-double excitations in the CI leads to results that agree well with experiment and that do not change significantly with increasing active space for most organic molecules. Calculated second-order hyperpolarizabilities using this type of CI within a sum-over-states calculation appear to be of useful accuracy.

Application of a modified z-cosy experiment for the analysis of spectra of oriented molecules - the spectrum of cis,cis-mucanonitrile

NMR spectra of cis,cis-mucanonitrile oriented in a liquid crystal have been analysed using the connectivity information obtained from a modified Z-COSY experiment which provided crucial clues for the starting parameters for the iterative analysis. The proton spectra with and without C-13 satellites and the C-13 spectra have thus been interpreted. The indirect spin-spin couplings required for the analyses have been obtained from the corresponding isotropic spectra. The H-1-H-1 and C-13-H-1 dipolar couplings so obtained have been utilized to determine the relative internuclear distances. The results indicate that the molecule is planar. (C) 1994 Academic Press, Inc.

Contribution of solvent effect to the optical spectra of polyanilines: has it been underestimated

The coefficient of thermochromism of polyaniline solutions has been found to be solvent dependent and the solvent effect is not negligible. Hence, thermochromism of polyaniline solutions cannot be explained solely on the basis of conformational change induced by a change in temperature. Further, comparison of the solvatochromism of polyaniline and polytoluidine shows a higher solvatochromic shift for the former. It implies that the higher energy associated with the exciton peak of polytoluidine is not due to the higher ring torsional angle induced by the higher steric repulsion of the methyl group, as widely accepted, but is due to its less solvatochromic red-shift as compared to polyaniline.

Copper( 11) Complexes of Novel Tripodal Ligands containing Phenolate and Benzimidazole/Pyridine Pendants: Synthesis, Structure, Spectra and Electrochemical Behaviour

Mononuclear copper(II) complexes of tri- and tetra-dentate tripodal ligands containing phenolic hydroxyl and benzimidazole or pyridine groups have been isolated. They are of the type (CuL(X)].nH2O, [CuL(H2O)]X.nH2O or [CuL].nH2O where X = Cl-, ClO4-, N3- or NCS- and n = 0-4. The electronic spectra of all the complexes exhibit a broad absorption band around 14000 cm-1 and the polycrystalline as well as the frozen-solution EPR spectra are axial, indicating square-based geometries. The crystal structure of [CuL(Cl)] [HL = (2-hydroxy-5-nitrobenzyl)bis(2-pyridyl-methyl)amine] revealed a square-pyramidal geometry around Cu(II). The mononuclear complex crystallises in the triclinic space group P1BAR with a = 6.938(1), b = 11.782(6), c = 12.678(3) angstrom and alpha = 114.56(3), beta = 92.70(2), gamma = 95.36(2)-degrees. The co-ordination plane is comprised of one tertiary amine and two pyridine nitrogens and a chloride ion. The phenolate ion unusually occupies the axial site, possibly due to the electron-withdrawing p-nitro group. The enhanced pi delocalisation involving the p-nitrophenolate donor elevates the E1/2 values. The spectral and electrochemical results suggest the order of donor strength as nitrophenolate < pyridine < benzimidazole in the tridentate and nitrophenolate < benzimidazole < pyridine in the tetradentate ligand complexes.

Ab initio studies of the structure and vibrational spectra of methyl isocyanide-borane and acetonitrile-borane

The SCF/DZP and MP2/DZP methods of ab initio quantum chemistry have been utilized to study the structure, vibrational spectra, binding energy, and barrier to internal rotation of methyl isocyanide-borane and acetonitrile-borane adducts. The eclipsed conformation of the complexes was predicted to be a minimum, and the staggered form is a transition state with a barrier height of about 10 cal/mol. The vibrational analyses of CH3NC-BH3 and CH3CN-BH3 and several of their isotopomers have been carried out by the GF matrix method. Computations have also been carried out for free CH3NC and CH3CN in order to investigate the changes in CH3NC and CH3CN as a result of their complex formation with BH3. To obtain an acceptable set of force constants, a recently proposed procedure ''RECOVES'' has been utilized. The increase in the N=C/C=N stretching force constant of CH3NC/CH3CN on adduct formation is interpreted with the help of Parr and Borkman's model. The binding energies for the two adducts have been determined taking basis set superposition error (BSSE) into consideration. The effect of the BSSE on structure, dipole moment, and vibrational frequencies of CH3CN and CH3NC is also evaluated. The predicted infrared band intensities for the two complexes are in good agreement with the experimentally observed features, and they have been utilized in the assignment of vibrational frequencies.