Vibrational spectra of several nitramines in the long-wave region (50–450 cm−1) were studied. The frequencies of intra- and intermolecular vibrations were separated and a tentative assignment of the frequencies
of self-associative complexes was performed.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2241–2244, November, 1998. 相似文献
Surface tension measurements can be used to investigate molecular complex formation in liquid solutions for strong and weak
complexes. The association constant and epthalpy for triethylamine-iodine, hexamethylbenzene-tetracyanoethylene and ethanol-iodine
in cyclohexane are 4·55×103, 218 and 0.93M−1 at 25° C and 12·5, 7·7 and 5·1 kcal/mol respectively. These values compare well with those reported in the literature by
other methods. 相似文献
Coupling of alkynylbenzoyl systems with γ,δ-unsaturated Fischer carbene complexes leads to the formation of hydrophenanthrene derivatives. This reaction is not affected by aqueous systems, which offer a further advantage such that chromium hexacarbonyl sublimes during the reaction process. Chromium carbene-alkyne coupling processes can thus be performed in environmentally friendly solvents with substoichiometric net consumption of chromium hexacarbonyl. 相似文献
Aspects of intramolecular light energy and electron transfer are discussed for three protein cofactor complexes whose three-dimensional structures have been elucidated by X-ray crystallography: the light harvesting phycobilisomes of cyanobacteria, the reaction center of purple bacteria, and the blue multi-copper oxidases. A wealth of functional data is available for these systems which allows specific correlations to be made between structure and function and general conclusions to be drawn about light energy and electron transfer in biological materials. 相似文献
Novel [CrIII(amp)(bipy)(Cl)] (1) (H2amp = N-(hydroxyphenyl)salicyldimine; bipy = 2,2-bipyridyl) and [CrIII(app)(bipy)(Cl)]+ (2) (H2app = N-(hydroxyphenyl)pyridine-2-carboxaldimine; bipy = 2,2-bipyridyl) complexes have been synthesized and characterized by physico-chemical methods. Complexes 1 and 2 have been employed as catalysts in the oxidation of both saturated and unsaturated hydrocarbons using tert-butylhydroperoxide (t-BuOOH). The significance of the results with respect to oxo-functionalization of C-H bonds both in unsaturated and saturated hydrocarbons is noted. 相似文献
The mixed-ligand p-hydroxybenzoate complexes of Ni(II), Cu(II) and Zn(II) with nicotinamide and N,N-diethylnicotinamide were synthesized and
characterized by elemental analysis, magnetic susceptibility measurements and mass spectrometry. The thermal behavior of the
complexes was studied by simultaneous TG, DTG and DTA methods in static air atmosphere. The infrared spectral characteristics
of the complexes are also discussed. The complexes contain two water molecules, two p-hydroxybenzoato (p-hba) and two nicotinamide (na) (or diethylnicotinamide (dena)) ligands per formula unit. In these complexes,
all ligands are coordinated to the metal ion as monodendate ligands. In Zn(II)-na and Cu(II)-dena complexes, thep-hydroxybenzoate behaves as bidentate chelating ligand through carboxylic oxygen atoms. The decomposition pathways and the
stability of the complexes are interpreted in the terms of the structural data. The final decomposition products were found
to be the respective metal oxides.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
In this work, 4-diethanolaminomethyl styrene (DEAMSt) monomer was prepared by modification of 4-chloromethyl styrene with diethanolamine. The homopolymerization of styrene modificated was carried out by free radical polymerization method at 60?°C in presence of 1,4-dioxane and AIBN. The metal complexes were prepared by reaction of the homopolymer used as ligand P(DEAMSt)Ll and Ni(II), Co(II) metal ions in presence of ethanol and dilute NaOH at 65?°C for 48?h in pH 6.
The structure of modificated monomer, homopolymer used as ligand and polymer-metal complexes were characterized by (FT-IR), 1H-NMR, 13C-NMR, Raman spectroscopy tecniques, elemental analysis, SEM, XRD and magnetic measurements. Their geometric structures according to magnetic measurements of Co(II) and Ni(II) complexes were estimated that have a tetrahedral structure. P(DEAMSt)Ll polymer has a transition state between amorphous and crystalline, whereas metal complexes (Co(II) and Ni(II) are with a large crystal structure. The molecular weight of P(DEAMSt)L1 homopolymer was determined by gel permeation chromatography (GPC). The glass transition temperature (Tg) of homopolymer was measured by differantial scanning calorimeter (DSC). The thermal behaviors of both ligand and polymer-metal complexes were investigated by thermogravimetric analysis (TGA) and (DTA). The results obtained were compared with each other. Then, the dielectrical measurements (dielectric constant, dielectric loss and conductivity) of the ligand and polymer-metal complexes were investigated as a function of temperature and frequency. The activation energies (Ea) of the ligand and metal complexes were determined from the conductivity measurements. 相似文献
Nicke(II) chloride reacts with N,N′-diarylformamidino-N′-arylcarbamides thiocarbamides and N-benzoylformamidino-N′-arylcarbamides,
thiocarbamides forming complexes of the general formula [Ni (Ar.NH.C (NH) NH.C.X. NH.R)2] Cl2 (R=phenyl, orthotolyl and paratolyl; Ar=benzoyl; X=S,O) and [Ni (R.NH.C.X.NH.C (N.Ph.).NH.Ph.)2] Cl2 (R=phenyl, orthotolyl, paratolyl; Ph=phenyl; X=S, O). The ligands when oxidized with iodine undergo ring closure to related
3,5-diarylamino 1,2,4-thiadiazolidines and 3,5-diarylamino-1,2,4-diazolidines, while the complexes are not susceptible to
oxidation. This confirms the binding in complexes is through sulphur and oxygen of the ligands. 相似文献
An ion-exchange method was used to determine complexation constants for the Ni-oxalate and Ni-carbonate systems in a NaClO4 background electrolyte. The Ni-oxalate data were interpreted in terms of a single Niox(aq) complex having log K1 values for Ni2+ + ox2– Niox(aq) of 3.9 ± 0.1 (I.S. = 0.5 mol-L–1 p[H] = 7.1) and 4.4 ± 0.1 (I.S. = 0.1 mol-L–1 p[H] = 8.6) at 22 ± 1C. Specific ion-interaction theory (SIT) was used to obtain log K1 = 5.17 ± 0.05 (95% confidence level and = –0.23 ± 0.15) at I.S. = 0. The Ni-carbonate studies were carried out at p[H] values of 7.5, 8.5, and 9.6 in 0.5 mol-L–1 NaClO4/NaHCO3 solutions. The NiCO3(aq) species was the dominant complex in the [CO32–] concentration ranges studied at all three p[H] values. A log K1 value for Ni2+ + CO32– NiCO3(aq) of 2.9 ± 0.3 was deduced at I.S. = 0.5 mol-L–1. Extrapolating this value to zero ionic strength using the SIT approach yielded log K1 = 4.2 ± 0.3 (95% confidence level and = –0.26 ± 0.04). The data allowed upper bound values for the complexation constants for NiHCO3+ and Ni(CO3)22– to be estimated, i.e., log K < 1.4 for Ni2+ + HCO3– NiHCO3+, and log K2 < 2 for NiCO3(aq) + CO32– Ni(CO3)22–, respectively. 相似文献