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1.
Panina N. S. Belyaev A. N. Simanova S. A. 《Russian Journal of General Chemistry》2003,73(12):1835-1838
The most stable hydrolysis products of cis-[Pt(NH3)2(H2O)2]2
+ were revealed by means of DFT quantum-chemical calculations of this complex and its deprotonated forms with full geometry optimization. The resulting force fields and normal mode vibrations were used to calculate thermodynamic characteristics for possible hydrolysis stages and equilibrium constants for proton-transfer processes in the gas phase and in aqueous solutions. The hydroxo-bridged dimers [Pt(NH3)2(-OH)]2
2
+ with short Pt+++Pt distances are the hydrolysis products of platinum(II) cis-diaquadiamminates in the aqueous medium. 相似文献
2.
Bokach NA Kuznetsova TV Simanova SA Haukka M Pombeiro AJ Kukushkin VY 《Inorganic chemistry》2005,44(14):5152-5160
Treatment of trans-[PtCl4(RCN)2] (R = Me, Et, Ph, NEt2) with 2 equiv of the amidine PhC(=NH)NHPh in a suspension of MeCN (R = Me), CHCl3 (R = Et, Ph), or in CHCl3 solution (R = NEt2) results in the formation of the imidoylamidine complexes trans-[PtCl4{NH=C(R)N=C(Ph)NHPh}2] (1-4) isolated in good yields (66-84%). The reaction of soluble complexes 3 and 4 with 2 equiv of Ph3P=CHCO2Me in CH2Cl2 (40 degrees C, 5 h) leads to dehydrochlorination resulting in a chelate ring closure to furnish the platinum(IV) chelates [PtCl2{NH=C(R)NC(Ph)=NPh}2] (R = Ph, 5; R = NEt2, 6), accordingly, and the phosphonium salt [Ph3PCH2CO2Me]Cl. Treatment of 5 with 3 equiv of Ph3P=CHCO2Me at 50 degrees C for 5 d resulted in only a 30% conversion to the corresponding Pt(II) complex [Pt{NH=C(NEt2)NC(Ph)=NPh}2] (15). The reduction can be achieved within several minutes, when Ph2PCH2CH2PPh2 in CDCl3 is used. When the platinum(II) complex trans-[PtCl2(RCN)2] is reacted with 2 equiv of the amidine, the imidoylamidinato complexes [PtCl(RCN){NH=C(R)NC(Ph)=NHPh}] (8-11) and [PhC(=NH)NHPh] x HCl (7) are formed. The reaction of trans-[PtCl2(RCN)2] with 4 equiv of the amidine under a prolonged reaction time or treatment of [PtCl(RCN){NH=C(R)NC(Ph)=NHPh}] (8-11) with 2 more equiv of the amidine yields the complex bearing two chelate rings [Pt{NH=C(R)NC(Ph)=NHPh}2] (12-15). The treatment of cis-[PtCl2(RCN)2] (R = Me, Et) with the amidine gives ca. 50-60% yield of [PtCl2{NH=C(R)NHC(Ph)=NHPh}] (16 and 17). All of the platinum compounds were characterized by elemental analyses; FAB mass spectrometry; IR spectroscopy; 1H, 13C{1H}, and 195Pt NMR spectroscopies, and four of them (4, 6, 8, and 15) were also characterized by X-ray crystallography. The coupling of the Pt-bound nitriles and the amidine is metal-mediated insofar as RCN and PhC(=NH)NHPh do not react in the absence of the metal centers in conditions more drastic than those of the observed reactions. The nitrile-amidine coupling reported in this work constitutes a route to the synthesis of imidoylamidine complexes, some of them exhibiting luminescent properties. 相似文献
3.
Belyaev A. N. Simanova S. A. Gorlov M. Yu. Bashmakov V. I. Panina N. S. Vyatkin V. E. 《Russian Journal of General Chemistry》2001,71(8):1186-1193
Chemical and electrochemical oxidation of rhodium (III) oxo-bridged carboxylate complexes was studied. The chemical [with O3 and Ce(IV) salts] or electrochemical (at potentials of 1.00-1.20 V) oxidations of the binuclear complexes [Rh2(-O)(-O2CCH3)2(H2O)6]2
+ and [Rh2(-O)(-O2CCF3)2(H2O)6]2
+ leads to the superoxo complexes [Rh2(-O)(O2-)(-O2CCH3)2(H2O)5]+ and [Rh2(-O)(O2
-)(-O2CCF3)2(H2O)5]+ with terminal coordination of O2-. The trinuclear acetate [Rh3(3-O)(-O2CCH3)6(H2O)3]+, unlike its trifluoroacetate analog [Rh3(3-O)(-O2CCF3)6(H2O)3]+, is oxidized only electrochemically at a potential of 1.38 V. The oxidation of [Rh3(3-O)(-O2CCH3)6(H2O)3]+ is reversible and involves formation of an unstable superoxo group O2
- between two Rh3III(3-O) cores. 相似文献
4.
S. A. Simanova T. V. Kuznetsova L. V. Konovalov A. V. Shchukarev 《Russian Journal of Applied Chemistry》2005,78(5):715-721
Sorption of platinum(II) and platinum(IV) chloride complexes on nitrogen-containing fibrous sorbents derived from polyacrylonitrile with aminoguanidine groups (GLIPAN-3) was studied as influenced by the temperature, platinum concentration in the solution, and pH of the solution. The kinetic sorption parameters and the sorption capacities of the sorbents in hydrochloric acid and chloride solutions were determined. The sorption mechanism and the composition of platinum compounds formed in the sorbent phase were suggested.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 5, 2005, pp. 729–735.Original Russian Text Copyright © 2005 by Simanova, Kuznetsova, Konovalov, Shchukarev. 相似文献
5.
N. V. Abovskaya S. A. Simanova E. S. Boichinova M. K. Fedorov 《Russian Journal of Applied Chemistry》2006,79(4):563-567
The sorption on a hydrated zirconium(IV) dioxide from solutions of trinuclear iridium(IV,IV,IV) and iridium(III,III,IV) oxosulfates was studied. The effect of temperature, sorbent grain size, concentration of sulfate complexes of iridium in solution, and acidity of the medium on the sorption recovery was considered. 相似文献
6.
1,10-Phenanthroline, 2,2′-bi-1,10-phenanthroline, and its dianion were examined by DFT B3LYP calculations in the 6-31G** basis set using the GAMESS-2006 program complex. The rigid tetradentate heterocycle, 2,2′-bi-1,10-phenanthroline, in the reduced electron-excessive form L2? creates more favorable geometric and electronic conditions for insertion of complexing ions in its cavity, compared to the neutral ligand. 相似文献
7.
V. N. Demidov S. A. Simanova A. I. Savinova A. V. Zinchenko T. B. Pakhomova E. A. Aleksandrova 《Journal of Structural Chemistry》2010,51(2):296-302
A neutral complex of palladium(II) with 2,9-dimethyl-1,10-phenanthroline [Pd(2,9-Me2-phen)Cl2] (goldish orange colored) is examined by single crystal X-ray diffraction. The crystals of [Pd(2,9-Me2-phen)Cl2] are monoclinic and belong to the space group P21/n (a = 11.8670(7) Å, b = 7.8195(5) Å, c = 14.2418(9) Å, β = 92.5450(10)°, Z = 4, V = 1320.25 Å3, R = 0.0289). The complex [Pd(2,9-Me2-phen)Cl2] exhibits a strong distortion of the usual square-planar geometry with a deviation of the central Pd2+ ion and two chloride acido-ligands from the plane of coordinated 2,9-dimethyl-1,10-phenanthroline. The lengths of two Pd-N bonds are slightly different and are 2.058 Å and 2.067 Å, the lengths of the Pd-Cl bonds are equal and are 2.285 Å. 2,9-Me2-phen itself also suffers some distortion of the planar geometry resulting in the boat conformation of the molecule. The crystal structure of the [Pd(2,9-Me2-phen)Cl2] complex is characterized by the presence of π-π stacked dimers arranged in infinite tilted stacks. 相似文献
8.
D. S. Ruzanov A. I. Fisher A. V. Eremin V. G. Antonov O. S. Fedorova M. A. Stepanova A. N. Belyaev S. A. Simanova 《Russian Journal of Applied Chemistry》2008,81(5):904-905
Catalytic activity of oligonuclear cobalt(III) and cobalt(II, III) oxoacetate complexes in homogeneous oxidation of glutathione with hydrogen peroxide was studied. 相似文献
9.
M. V. Afonin S. A. Simanova N. M. Burmistrova N. S. Panina Yu. A. Karpov O. A. Dal’nova 《Russian Journal of Applied Chemistry》2008,81(11):1933-1938
The recovery of platinum(II) and platinum(IV) chloro complexes from hydrochloric acid and chloride solutions with a new heterochain S,N-containing sorbent, MITKhAT, was studied. The suggested mechanism of formation of platinum(II) mercapto-thio ether complexes in the course of sorption was confirmed by DFT calculations. The results of group and selective recovery of platinum metals with MITKhAT sorbent from simulated and real industrial solutions are reported. 相似文献
10.
A. I. Fischer D. O. Ruzanov M. Yu. Gorlov A. V. Shchukarev A. N. Belyaev S. A. Simanova 《Russian Journal of Coordination Chemistry》2007,33(11):789-794
A new octanuclear mixed-valence cobalt acetate complex of the cationic type [Co4 IICo4 III(μ4-O)4(μ3-OMe)4(μ-OAc)6(H2O)8]F2 · 10H2O ([I]F2 · 10H2O) was prepared by crystallization from a solution of ‘cobalt(III) acetate’ in a Me2CO-MeOH-H2O-HF mixture and studied by X-ray diffraction. The crystals are monoclinic: space group C2/c, a = 17.222 Å, b = 16.836 Å, c = 16.586 Å, β = 94.902°, Z = 4, R = 4.37% (I > 2σ(I)). In the crystal, the I2+ complex cations, fluoride anions, and solvate water molecules form a three-dimensional (3D) coordination supermolecular system. 相似文献