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31.
Tetra-coordinated boron derivatives, (EtO)B(DTZ) and (DTZH)B(DTZ), (where DTZ−− and DTZ− represent the anions of the Schiff base DTZH2) have been synthesized by 1:1 and 1:2 molar reactions of triethoxyborane with bibasic tridentate Schiff bases, derived by
the equimolar condensation of S-methyl or S-benzyldithiocarbazate with acetyl acetone or benzoyl acetone. Further 1:1 derivatives
have been shown to undergo replacement reactions witht-butyl alcohol, showing thereby the labile nature of the ethoxy group. Based on infrared and proton magnetic resonance spectral
studies and monomeric nature, suitable structures have been assigned to these derivatives. 相似文献
32.
Tapan Kumar Lal John F. Richardson Mark S. Mashuta Robert M. Buchanan Rabindranath Mukherjee 《Polyhedron》1997,16(24):1248-4336
Synthesis and characterization of a nitrite-bound copper(II) compound [CuL4)2(ONO)]ClO4 have been achieved (L4 = 2-(3,5-dimethylpyrazol-1-ylmethyl)pyridine]. The bidentate ligand L4 provides a pyridine and a pyrazole donor site; however, they are separated by a methylene spacer. The complex has been structurally characterized and it belongs to only a handful of complexes having nitrito-bound mononuclear copper(II) centre. The metal atom has a distorted square pyramidal geometry with the copper atom displaced from the equatorial plane by 0.25 Å. In MeCN solution the green complex exhibits a broad ligand-field transition at 655 nm with a shoulder at 675 nm and in dichloromethane-toluene glass (80 K) it exhibits an EPR spectral feature characteristic of the unpaired electron in the dx2−y2 orbital. Variable-temperature (80–300 K) magnetic susceptibility measurements in the solid state as well as room temperature measurement in MeCN solution reveal mononuclear magnetically dilute copper(II) centre. When examined by cyclic voltammetry (MeCN solution) it displays electrochemically irreversible CuII---CuI response [cathodic peak potential, Epc (V vs saturated calomel electrode (SCE)): −0.32]. An oxidative response is observed at 1.14 V, probably due to bound-nitrite oxidation and is partially removed to generate a solvated complex at the electrode surface. The latter species gives rise to reversible CuII---CuI redox response [
]. 相似文献
33.
Emission and absorption polarization spectra as well as emission lifetimes between room temperature and 5 °K have been measured of [Cr urea6]X3 single crystals, where X stands for ClO
4
–
, J–, NO
3
–
, Br–, Cl–, F–, and X3 for JSO
4
3–
. The strong temperature dependence of the fluorescence/phosphorescence-ratios, and of the emission lifetimes is discussed. The differences between the spectra as well as the emission lifetimes of the various salts can be attributed to an anion dependent trigonal perturbation.
Die Autoren danken dem Verband der Chemischen Industrie für finanzielle Unterstützung dieser Arbeit. 相似文献
34.
James O. Jensen 《Journal of Molecular Structure》2004,686(1-3):165-172
The normal mode frequencies and corresponding vibrational assignments of phosphirane in are examined theoretically using the GAUSSIAN 98 set of quantum chemistry codes. All normal modes were successfully assigned to one of nine types of motion (C–C stretch, P–C stretch C–H stretch, P–H stretch, CH2 scissors, CH2 wag, CH2 rock, CH2 twist, and P–H wag) predicted by a group theoretical analysis. Comparing the vibrational frequencies with IR and Raman spectra available in the literature, a set of scaling factors are derived. Predicted infrared and Raman intensities are reported. 相似文献
35.
A. V. Afonin 《Russian Chemical Bulletin》1996,45(5):1142-1144
The analysis of the effect of the solvents on the proton chemical shifts in1H NMR spectra of 2-vinyloxypyridine indicates that the C—H...N interaction of weak intramolecular hydrogen bond type hinders the formation of intermolecular hydrogen C—H...X and C-H... bonds. The protonating solvents reduce the intramolecular C—H...N interaction due to association with the N atom of the pyridine cycle.Translated fromIzvestiya Akademii Nauk. Seriya Khimieheskaya, No. S, pp. 1202–1204, May, 1996. 相似文献
36.
S. V. Volkov S. V. Kutyakov A. N. Levov E. I. Polyakova Le Tuan An S. A. Soldatova P. B. Terentiev A. T. Soldatenkov 《Chemistry of Heterocyclic Compounds》2007,43(10):1260-1268
It has been established that on heating, 3-benzoyl-4-hydroxy-1-methyl-4-phenylpiperidine is ring-opened in the presence of
arylamines by a type of retroaldol reaction, with subsequent transamination of the intermediate Mannich base and the formation
of 3-arylamino-1-oxo-1-phenylpropanes. When using arylhydrazines this γ-piperidol is recyclized with the formation of 1,3-diarylpyrazoles
and their 4,5-dihydro derivatives. The mass spectral behavior of a series of 3-arylamino-substituted 1-phenylpropanones has
been studied.
__________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1486–1495, October, 2007. 相似文献
37.
Electronic structure and conformation of N-amino-2,5-dimethylpyrrole derivatives and N-formylaniline
V. V. Zverev 《Russian Chemical Bulletin》1992,41(3):474-477
From photoelectronic spectroscopy data N-amino-, N-dimethyl-, N-methylphenyl-, and N-methylformylamino-2,5-dimethylpyrrole molecules were found to have an acoplanar-oriented fragment conformation in the gas phase, while N-formylaniline had a planar structure. In aminopyrroles the n-n repulsion energy of unshared pairs exceeded the n-* conjugation energy.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences, Kazan 420083. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 602–606, March, 1992. 相似文献
38.
A. A. Bezrukova V. S. Khandkarova P. V. Petrovskii A. Z. Rubezhov Ya. S. Vygodskii K. P. Butin T. V. Magdesieva G. A. Pirogova 《Russian Chemical Bulletin》1995,44(5):941-945
Binuclear RhIII and RuII complexes of the [M1-CN-M2]+BF
4
–
(M1 and/or M2 are (5-Cp)(3-C3H5)Rh and (6-C6H6)(3-C3H5)Ru) type, heteronuclear organometallic compound (5-Cp)(3-C3H5)RhCNPd(3-C3H5)Cl, and mononuclear RhIII and RuII complexes [(3-C3H5)LM(MeCN)]+
BF4
–
(M = Rh, L = 5-Cp; M = Ru, L = 6-C6H6) were synthesized. An electrochemical study of these compounds in solutions demonstrates that the bond between the bridged CN ligand and the metal atoms is rather strong, and there is no dissociation into mononuclear fragments in solutions. The kinetics of the reaction of [(5-Cp)(3-C3H5)Rh(MeCN)]+
BF4
–
with halide ions was studied by electrochemical methods. The ligand exchange proceeds by a bimolecular dissociative-exchange mechanism.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 968–973, May, 1995. 相似文献
39.
The thermal decomposition of Co(NO3)2·6H2O (1) as well as that one of NO[Co(NO3)3] (Co(NO3)2·N2O4) (2) was followed by thermogravimetric (TG) measurements, X-ray recording and Raman and IR spectra. The stepwise decomposition reactions of 1 and 2 leading to anhydrous cobalt(II)nitrate (3) were established. In N2 atmosphere, cobalt oxides are finally formed whereas in H2/N2 (10% H2) cobalt metal is produced. Rapid heating of cobalt(II)nitrate hexahydrate causes melting (formation of a hydrate melt) and therefore side reactions in the hydrate melt by incoupled reactions and evolution/evaporation of different species as, e.g., HNO3, NO2, etc. In case of larger amounts in dense packing in the sample container, the formation of oxo(hydoxo)nitrates is possible at higher temperature. For 2, its thermal decomposition to 3 was followed and its decomposition mechanism is proposed. 相似文献
40.
The structure and conformational stability of ethyl pseudohalides CH3CH2 — XCN (X = O, S, Se) were investigated using ab initiocalculations at the MP2 level of theory with a triple- basis set augmented with polarization and diffusion functions. Full optimization was performed on the minimum energy structures as well as on the transition state forms. The relative stabilities of rotational conformers were calculated at the MP4 level using MP2 optimized reference geometries. The nature of all considered stationary points was verified by calculation of the harmonic vibrational frequencies. The calculated bond lengths, bond angles, dipole moments, and rotational constants of optimized global minima structures agree very well with the corresponding experimental data obtained from microwave spectroscopic studies. Also, available experimental frequencies are in good accord with the theoretical values. For ethyl cyanate CH3CH2 — OCN, the antiperiplanar (trans) form is predicted to be more stable than the synclinal (gauche) form, and the synperiplanar (cis) form corresponds to the transition state. For both ethyl thiocyanate CH3CH2 — SCN and ethyl selenocyanate CH3CH2 — SeCN, the gaucheform is the global minimum while the trans-conformer is a local minimum and the cis-form is a transition state. 相似文献