共查询到20条相似文献,搜索用时 31 毫秒
1.
E. A. Kovalenko D. A. Mainichev O. A. Gerasko D. Yu. Naumov V. P. Fedin 《Russian Chemical Bulletin》2011,60(5):841-848
Inclusion compounds of the macrocyclic cavitand cucurbit[8]uril (CB[8], C48H48N32O16) with the copper(ii) and zinc(ii) complexes with the tetraazamacrocyclic ligand cyclam, {[Cu(cyclam)(H2O)2]@CB[8]}Cl2·18H2O (1) and {[Zn(cyclam)]@CB[8]}Cl2·13H2O (2), were synthesized. The compounds were characterized by X-ray diffraction analysis, electrospray mass spectrometry, IR spectroscopy,
and elemental analysis. The 1H and 13C NMR method revealed only one trans-isomer of the zinc(ii) complex with cyclam in an aqueous solution of inclusion compound 2. 相似文献
2.
T. N. Kropacheva V. I. Kornev D. A. Loginov V. I. Meshcheryakov E. V. Mutseneck D. V. Muratov D. S. Perekalin L. S. Shul’pina A. R. Kudinov 《Russian Chemical Bulletin》2005,54(10):2354-2358
New dinuclear ruthenium manganese complexes of general composition (bpy)2Ru(L)MnClx(H2O)2 (L is 1,10-phenanthroline-5,6-dione, 3,3′-dicarboxy-2,2′-bipyridyl, or bis(pyrazolyl); x = 2 or 4) were synthesized by the reaction of (bpy)2Ru(L) with MnCl2 · 4H2O. These compounds and the starting mononuclear ruthenium complexes were studied by spectrophotometric and electrochemical
methods in MeCN. The position of the charge-transfer band RuII → L in the spectra depends on the donor-acceptor characteristics of the ligand L. For the dinuclear complex under study,
the formal potentials of reversible one-electron oxidation of RuII are in the range of 0.9–1.2 V (vs. the standard hydrogen electrode), whereas oxidation of MnII occurs at more positive (by 0.1–0.2 V) potentials.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2281–2285, October, 2005. 相似文献
3.
T. V. Mitkina D. Yu. Naumov N. V. Kurat’eva O. A. Gerasko V. P. Fedin 《Russian Chemical Bulletin》2006,55(1):26-35
Inclusion compounds of the macrocyclic cavitand cucurbit[8]uril (CB[8]) with the nickel(II) complex, {trans-[Ni(en)2(H2O)2]@CB[8]}Cl2 · 23.5H2O, the copper(II) complex, {2[Cu(dien)(bipy)(H2O)]@CB[8]}(ClO4)4 · 11H2O, and the organic molecules, 2(pyCN)@CB[8]} · 16H2O and {2(bpe)@CB[8]} · 17H2O, where bipy is 4,4′-bipyridyl, pyCN is 4-cyanopyridine, and bpe is trans-1,2-bis(4-pyridyl)ethylene, were synthesized. The inclusion compounds with organic molecules were synthesized starting from
inclusion compounds of cucurbit[8]uril with cyclam and ethylenediamine complexes of copper(II) and nickel(II) by the guest exchange method, which is based on the replacement of one guest with another in the cavity of the cavitand
The resulting compounds were characterized by X-ray diffraction, ESR, 1H NMR, IR, and electronic absorption spectroscopy, and electrospray mass spectrometry. Photochemically induced [2+2]-cycloaddition
of two 1,2-bis(4-pyridyl)ethylene molecules included in cucurbit[8]uril was studied.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 25–34, January, 2006. 相似文献
4.
G. M. Larin A. N. Gusev Yu. V. Trush K. V. Rabotyagov V. F. Shul’gin G. G. Aleksandrov I. L. Eremenko 《Russian Chemical Bulletin》2007,56(10):1964-1971
Spacer-armed dinuclear copper(II) complexes with condensation products of isophthalic and terephthalic acid dihydrazides with salicylaldehyde and 2-hydroxyacetophenone
were synthesized and studied by EPR and X-ray diffraction. The compositions and structures of most of the complexes were determined
by elemental analysis, thermogravimetric analysis, and IR spectroscopy. The structure of the copper(II) complex with acyldihydrazone of salicylaldehyde and 1,3-benzenedicarboxylic acid (H4L) with the composition [Cu2L1·2morph·MeOH] (morph is morpholine) was established by X-ray diffraction. The CuII atoms are spaced by 10.29 Å and are structurally nonequivalent. One copper cation has a square-planar coordination formed
by donor atoms (2 N + O) of the doubly deprotonated acylhydrazine fragment and the N atom of the morpholine molecule. The
second copper atom is additionally coordinated by a methanol molecule through the oxygen atom, so that this copper atom is
in a tetragonal-pyramidal coordination with the oxygen atom in the axial position. The EPR spectra of liquid solutions of
the complexes based on 1,4-benzenedicarboxylic acid acyldihydrazones and 1,3-benzenedicarboxylic acid bis(salicylidene)hydrazone
at room temperature show a four-line hyperfine structure with the constant a
Cu = 54.4–67.0·10−4 cm−1 (g = 2.105–2.147), which is indicative of the independent behavior of the paramagnetic centers. The EPR spectrum of a solution
of the complex based on isophthalic acid and 2-hydroxyacetophenone shows the seven-line hyperfine structure corresponding
to two equivalent copper nuclei (g = 2.11, a
Cu = 36.5·10−4 cm−1).
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1898–1905, October, 2007. 相似文献
5.
Dinuclear copper(II) complexes with acyldihydrazones of 2-hydroxy-5-nitroacetophenone (H4L) of the composition Cu2(Py)xL·mEtOH were synthesized and characterized. In these complexes, the coordination polyhedra of the copper atoms are linked to
each other by a polymethylene chain of different lengths, from one to five monomer units. The structure of the [Cu2L·4Mrf] complex (Mrf is morpholine) based on acyldihydrazone of malonic acid was established by X-ray diffraction. The copper(II) atoms in this complex are [4+1]-coordinated and are spaced by 6.94 Å. At room temperature, the signal in the ESR spectra
of solutions of the complexes based on acyldihydrazones of malonic, succinic, glutaric, and adipic acids has a seven-line
hyperfine structure with the constant of (35.3–38.8)·10−4 cm−1 (g = 2.109–2.112) due to exchange interactions between unpaired electrons and two equivalent copper nuclei. An increase in the
length of the polymethylene chain to five monomer units hinders exchange interactions, and the ESR signal of the complex based
on acyldihydrazone of pimelic acid has a four-line hyperfine structure with a
Cu = 72.7·10−4 cm−1 typical of mononuclear copper(II) complexes.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 229–234, February, 2007. 相似文献
6.
E. A. Kovalenko T. V. Mitkina O. A. Gerasko D. Yu. Naumov D. G. Samsonenko V. P. Fedin 《Russian Chemical Bulletin》2010,59(11):2072-2080
Inclusion compounds of the macrocyclic cavitand cucurbit[8]uril (CB[8]) with the ruthenium(iii) bis(ethylenediamine) complex {trans-[Ru(en)2Cl2]@CB[8]}Cl·27.5H2O (1), the gold(iii) diethylenetriamine complex {[Au(dien)Cl]@CB[8]}Cl2·11H2O (2), and the gold(iii) and platinum(ii) cyclam complexes (H3O)5{[Au(cyclam)]@CB[8]}Cl8·18H2O (3) and {[Pt(cyclam)]0.11(H2cyclam)0.89@CB[8]}Cl2·16H2O (4), respectively, where cyclam is the tetraazamacrocyclic ligand, were synthesized. The inclusion compounds were synthesized
both directly starting from CB[8] and the metal complexes with polyamines (en or dien) and by the two-step method with the
use of the cyclic polyamine ligand (cyclam) pre-included into the cavity of the macrocycle. The inclusion compounds were characterized
by X-ray diffraction (1, 2, and 4), IR spectroscopy, electrospray ionization mass spectrometry, UV-Vis spectroscopy, and thermogravimetric analysis. 相似文献
7.
G. V. Romanenko S. E. Tolstikov E. V. Tretyakov S. V. Fokin V. N. Ikorskii V. I. Ovcharenko 《Russian Chemical Bulletin》2007,56(9):1795-1804
The reactions of bis(hexafluoroacetylacetonato)copper(II) [Cu(hfac)2] with the nitronyl nitroxide biradicals bis[4-(4,4,5,5-tetramethyl-3-oxide-1-oxyl-4,5-dihydro-1H-imidazol-2-yl)pyrazol-1-yl]alkanes (L6, L10, and L12) produced the framework heterospin complex [Cu(hfac)2]2L6 and the layer-polymeric heterospin complexes [Cu(hfac)2]2L10 and {[Cu(hfac)2]2L12} [Cu(hfac)2(PriOH)2], respectively. In the solid state of these compounds, the stereochemical nonrigidity is manifested as a deformation of the
polymethylene fragments-(CH2)n-.
Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1732–1741, September, 2007. 相似文献
8.
The hexanuclear complex [Fe6(O)2(CH2O2) (OOCCMe3)12 (THF)2]·THF was synthesized. The characteristic feature of this complex is the presence of the methanedithiolate bridge.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 795–797, March, 2005. 相似文献
9.
V. Ya. Kavun A. E. Panasenko L. A. Zemnukhova A. B. Slobodyuk 《Russian Chemical Bulletin》2008,57(7):1379-1383
Ionic mobility in the NaSbClF3 · H2O, KSbClF3, and NH4SbClF3 fluorochloride complexes was studied by 1H and 19F NMR spectroscopy in the temperature interval from 150 to 480 K. The types of ionic motions in the compounds were determined.
Their physicochemical characteristics were compared with those of the earlier studied sodium, potassium, and ammonium tetrafluoroantimonates(iii). The replacement of one F atom by the Cl atom in MSbF4 (M = Na, K, NH4) changes both the structure of the Sb polyhedra forming the structure of the antimony(iii) fluorochloride complex and the character of ionic motions in the compounds. The ionic conductivity in the 324–436 K range
was determined for NH4SbClF3: σ = 1.07 · 10−4 S cm−1 at T = 423 K.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1353–1357, July, 2008. 相似文献
10.
Kinetics of hydrogen peroxide decomposition in the presence of the tetraaquapalladium(II) complex in an aqueous solution at
40–70 °C was studied. The reaction rate is the first order with respect to the concentration of both PdII and H2O2 and the negative first order with respect to perchloric acid. Using free radicals traps, the reaction mechanism was found
to differ from the traditional free-radical mechanism known for d-metal aqua ions and proceeds without generation of hydroxyl
radicals. The kinetic data obtained suggest a mechanism involving the formation of an intermediate palladium complex with
oxygen.
__________
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1077–1082, May, 2005. 相似文献
11.
The sorption of anions H2PO4
−, HPO4
2−, PO4
3−, [Fe(CN)6]3−, and [Fe(CN)6]4− from aqueous solutions on the surface of FeIII and ZrIV oxyhydroxide hydrogels freshly precipitated at pH 4–13 was studied. The region of sorbate concentrations was from 0.00025
to 0.06 mol L−1. The plots of the anion uptakes vs. their equilibrium concentrations are represented by isotherms of the first type, which are well described by the Langmuir
equation if the quantity of the amount adsorbed is expressed as mol-site g−1. The maximum uptakes and constants of the Langmuir equation were calculated. The phosphate anions occupy the same number
of sorption sites on the sorbents precipitated at different pH. The average specific content of sorption sites for the ferro-
and zirconogels in the metastability period is independent of the pH of their precipitation, being 3.1·10−3 and 3.2·10−3 mol-site g−1, respectively. The [Fe(CN)6]3− and [Fe(CN)6]4− anions are sorbed only on the positively charged sites of the hydrogels and occupy not more than 2·10 mol-site g−1 in the studied interval of pH of precipitation.
__________
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1736—1741, August, 2005. 相似文献
12.
Critical phenomena in ethylbenzene oxidation in an acetic acid solution at high cobalt(III) concentrations (from 0.01 to 0.2 mol L−1) were studied at 60–90 °C by the gasometric (O2 absorption), spectrophotometric (CoIII accumulation), and chemiluminescence (relative concentration of radical RO2
·) methods. These phenomena are as follows: (1) increase in the oxidation rate above the theoretical limiting rate of radical
autooxidation (k
3
2[RH]2/2k
6); (2) achievement of a maximum and a sharp decrease in the oxidation rate and concentration of radical RO2
· with the further increase in the CoII concentration (existence of critical concentrations). The oxidation rate increases due to the reaction RO2
· + CoII + H+ → → ROOH + CoIII, while the inhibition effect is caused by the decay of RO2
· radical involving two cobalt(II) atoms: RO2
· + 2 CoII → R′CO + CoIII + CoII (k(70 °C) ≈ 300 L2 mol−2 s−1). The detailed scheme (through the formation of the complex RO2
·CoII) describing the conjugation of these reactions was proposed.
__________
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1823–1827, August, 2005. 相似文献
13.
L. O. Nindakova N. N. Chipanina V. K. Turchaninov M. V. Ustinov B. A. Shainyan 《Russian Chemical Bulletin》2005,54(10):2343-2347
The reaction of di-μ-chlorobis(1,5-cyclooctadiene)dirhodium with (4S, 5S)-2,2-dimethyl-4,5-bis(methylaminomethyl)-1,3-dioxolane (1) gave the complex [Rh(cod)(1)]Cl (cod is 1,5-cyclooctadiene). The composition of the complexes CoCl2 · L2 and [Rh(cod)(L2)]X (L2 = 1, (4S,5S)-2,2-dimethyl-4,5-bis(aminomethyl)-1,3-dioxolane, and (4S, 5S)-2,2-dimethyl-4,5-bis(dimethylaminomethyl)-1,3-dioxolane; X = Cl, TfO) was studied using IR and 1H NMR spectroscopy. In the RhI cyclooctadienediamine complexes, the diene molecule forms a stronger bond with the metal atom than that in the cyclooctadienediphosphine
analogs.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2270–2274, October, 2005. 相似文献
14.
Hasegawa H Fukushima T Lee JA Tsukamoto K Moriya K Ono Y Imai K 《Analytical and bioanalytical chemistry》2003,377(5):886-891
d-Lactic and l-lactic acids were simultaneously determined by means of a column-switching high-performance liquid chromatography (HPLC) with fluorescence detection. As a fluorescence reagent, 4-nitro-7-piperazino-2,1,3-benzoxadiazole (NBD-PZ) was employed for the fluorescence derivatization of lactic acid. The proposed HPLC system adopted both octylsilica (Cadenza CD-C8) and amylose-based chiral columns (CHIRALPAK AD-RH), which proved to give a sufficient enantiomeric separation of the lactic acid derivatives with a separation factor () of 1.32 and a resolution (Rs) of 1.98. Moreover, the features of the first elution of d-lactic acid peak in the proposed HPLC were convenient for the determination of trace amount of serum d-lactic acid, which is known to increase under diabetes. Intra-day and inter-day accuracies were in the range of 90.5–101.2 and 89.0–100.7%, and the intra-day and inter-day precisions were 0.3–1.2 and 0.4–4.8%, respectively. The proposed method was applied to determine d-lactic and l-lactic acids in human serum of normal subjects and diabetic patients, showing that both d-lactic and l-lactic acid concentrations were significantly increased in the serum of diabetic patients (n=31) as compared with normal subjects (n=21). This fact was found for the first time owing to the development of the proposed HPLC method which is able to determine d-lactic and l-lactic acid simultaneously. Finally, serum d-lactic acid concentrations determined by the proposed HPLC method were compared with those from a reported enzymatic assay, and the smaller p value between normal subjects and diabetic patients was shown by the proposed HPLC method. 相似文献
15.
The catalytic reduction of acetophenone, methyl α-acetamidocinnamate, and dimethyl itaconate with alcohol-modified sodium borohydride was studied in the presence of complexes CoCl2·L2 (L2 are chiral C
2-symmetric diamines: (4S,5S)-2,2-dimethyl-4,5-bis(aminomethyl)-1,3-dioxolane, (4S, 5S)-2,2-dimethyl-4,5-bis(methylaminomethyl)-1,3-dioxolane, (4S, 5S)-2,2-dimethyl-4,5-bis(dimethylaminomethyl)-1,3-dioxolane, and (4S, 5S)-2,2-dimethyl-4,5-bis(diphenylaminomethyl)-1,3-dioxolane). The maximum enantiomeric excess of (S)-1-phenylethanol was 24%, that of dimethyl α-methylsuccinate was 38%.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 342–347, February, 2005. 相似文献
16.
An enzymatic method for determining L-malic acid in wine based on an L-malate sensing layer with nicotinamide adenine dinucleotide (NAD+), L-malate dehydrogenase (L-MDH) and diaphorase (DI), immobilized by sol-gel technology, was constructed and evaluated. The sol-gel glass was prepared
with tetramethoxysilane (TMOS), water and HCl. L-MDH catalyzes the reaction between L-malate and NAD+, producing NADH, whose fluorescence (λ
exc = 340 nm, λ
em = 430 nm) could be directly related to the amount of L-malate. NADH is converted to NAD+ by applying hexacyanoferrate(III) as oxidant in the presence of DI. Some parameters affecting sol-gel encapsulation and the
pH of the enzymatic reaction were studied. The sensing layer has a dynamic range of 0.1–1.0 g/L of L-malate and a long-term storage stability of 25 days. It exhibits acceptable reproducibility [s
r(%)≈10] and allows six regenerations. The content of L-malic acid was determined for different types of wine, and polyvinylpolypyrrolidone (PVPP) was used as a bleaching agent
with red wine. The results obtained for the wine samples using the sensing layer are comparable to those obtained from a reference
method based on UV-vis molecular absorption spectrometry, if the matrix effect is corrected for. 相似文献
17.
E. Yu. Fursova O. V. Kuznetsova V. I. Ovcharenko G. V. Romanenko A. S. Bogomyakov M. A. Kiskin I. L. Eremenko 《Russian Chemical Bulletin》2007,56(9):1805-1808
A method was developed for the synthesis of mixed-metal heterospin compounds with the direct coordination of the nitroxide
fragment based on the replacement of acetonitrile molecules in the heterotrinuclear complex [Co2Gd(NO3)Piv6(CH3CN)2] with nitroxide molecules. The molecular and crystal structure of the heterospin mixed-ligand heterotrinuclear CoII, GdIII, CoII complex [Co2Gd(NO3)Piv6(NIT-Me)2], where NIT-Me is stable nitronyl nitroxide, was established. The magnetic properties of this complex were investigated in
the temperature range of 2–300 K. The coordination of nitroxide groups to CoII ions is responsible for strong exchange interactions between the unpaired electrons in the exchange clusters {>-·O-CoII}, resulting in the virtually complete spin coupling between each coordinated >N-·O group and one of the unpaired electrons
of each CoII ion at temperatures below 200 K.
Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1742–1745, September, 2007. 相似文献
18.
E. A. Kovalenko T. V. Mitkina O. A. Geras’ko D. G. Samsonenko D. Yu. Naumov V. P. Fedin 《Russian Journal of Coordination Chemistry》2011,37(3):161-167
New inclusion compounds containing iron(II), cobalt(III), and nickel(II) complexes with the cyclic polyamine ligands cyclam and cyclen in the macrocyclic cavitand cucurbit[8]uril (CB[8]) were obtained: {trans-[Fe(Cyclam)(CO)(OCHO)]@CB[8]}Cl · 15H2O, {cis-[Co(Cyclen)(H2O)Cl]@CB[8]}Cl2 · 20H2O, and {cis-[Ni(Cyclen)(H2O)Cl]@CB[8]}Cl · 12H2O. According to X-ray diffraction data, the complexes are in the cavity of each CB[8] molecule. The complexes of the above molecular formulas were isolated in the solid state as supramolecular compounds with CB[8] and structurally characterized for the first time. 相似文献
19.
A. V. Makarycheva-Mikhailova S. I. Selivanov N. A. Bokach V. Yu. Kukushkin P. F. Kelly A. J. L Pombeiro 《Russian Chemical Bulletin》2004,53(8):1681-1685
Reactions of the platinum(IV) nitrile complexes [PtCl4(RCN)2] (R = Me, CH2Ph, Ph) with 1,2- and 1,4-PhS(=NH)C6H4SPh in CH2Cl2 afforded addition products of sulfimides and coordinated nitriles, viz., the [PtCl4{NH=C(R)N=S(Ph)(C6H4SPh)}2] complexes. The latter were isolated in 75—90% yields and characterized by elemental analysis, positive-ion FAB mass spectrometry, IR spectroscopy, and 1H and 13C1H NMR spectroscopy. The temperature dependence of the 1H NMR spectra of the model [PtCl4{NH=C(R)N=SPh2}2] complexes (R = Me, Et) in CD2Cl2 studied in a temperature range from +40 to -70 °C demonstrated that E—Z isomerization of the ligands is a dynamic process in a range from +40 to -10 °C. The activation free energy of this process was calculated.Published in Russian in Izvestiya Akademii Nauk.
Seriya Khimicheskaya, No. 8, pp. 1618–1622, August, 2004. 相似文献
20.
E. K. Beloglazkina A. G. Majouga A. A. Moiseeva M. G. Tsepkov N. V. Zyk 《Russian Chemical Bulletin》2007,56(2):351-355
The reaction of 5-[2-(methylthio)ethyl]-3-phenyl-2-thioxoimidazolidin-4-one (LH) with salts MCl2· xH2O (M = Co, Ni, Cu; x = 2, 6) afforded the [M(L)Cl]n complexes of NiII, CoII, and CuII. The electrochemical behavior of the LH ligand and its complexes was studied using the cyclic voltammetry and rotating disk
electrode techniques. The structures of the synthesized compounds were determined by the data of UV—Vis and IR spectroscopy,
mass spectrometry, and electrochemical characteristics.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 339–343, February, 2007. 相似文献