共查询到20条相似文献,搜索用时 3 毫秒
1.
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
2.
E. K. Beloglazkina A. G. Majouga A. A. Moiseeva I. V. Yudin F. S. Moiseev O. I. Shmatova N. V. Zyk 《Russian Chemical Bulletin》2008,57(2):358-363
Transition metal (NiII, CoII, and CuII) complexes with 1,2-bis[2-(3-pyridylmethylideneamino)phenylthio]ethane (1) and 1,2-bis[2-(4-pyridylmethylideneamino)phenylthio]ethane (2) were synthesized for the first time by slow diffusion of solutions of compounds 1 or 2 in CH2Cl2 into solutions of MX2 · nH2O (M = Ni, Co, or Cu; X = Cl or NO3; n = 2 or 6) in ethanol. The reactions with CoII and CuII chlorides afford complexes of composition M(L)Cl2 (L = 1 or 2). The reactions of compound 1 with NiII salts produce complexes with 1,2-bis(2-aminophenylthio)ethane. The molecular structure of dinitrato[1,2-bis(2-aminophenylthio)ethane]nickel(ii) was confirmed by X-ray diffraction. The ligands and the complexes were investigated by cyclic voltammetry and rotating disk
electrode voltammetry. The initial reduction of the complexes proceeds at the metal atom. The oxidation of the chlorine-containing
complexes proceeds at the coordinated chloride anion.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 350–355, February, 2008. 相似文献
3.
E. K. Beloglazkina A. G. Majouga A. N. Chernysheva R. D. Rakhimov N. V. Zyk 《Russian Chemical Bulletin》2007,56(7):1374-1379
The reaction of 2,2′-di(2-hydroxybenzaliminoethyl) disulfide (H2L1) and 2-[(2-thioethyl)iminomethyl]phenol (H2L2) with MCl2·xH2O (M = Co, Ni, Cu) afforded the [M2(L1)Cl2] and [M(L2)]2 complexes, respectively. Their structures were determined by the data of electronic and IR spectroscopy and PM3 quantum chemical
calculations. The H2L1 ligand and the complexes were studied by electrochemistry (CV and using a rotating disk electrode). The primary electronic
changes are localized on the ligand fragment upon the electrochemical oxidation and reduction of the complexes.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1325–1330, July, 2007. 相似文献
4.
E. K. Beloglazkina I. V. Yudin A. G. Mazhuga A. A. Moiseeva S. V. Zatonskii N. V. Zyk 《Russian Chemical Bulletin》2008,57(3):577-584
A series of the M(L)Cl2 · nH2O and {M(L)}2(OAc)4 complexes (M = NiII, CoII, and CuII; L is 3- and 4-(2-pyridyl)-1,3-benzothiazole) were synthesized by the reaction of L with MX2 · nH2O (X = Cl, OAc) in ethanol. The molecular and crystal structures of the CuL2(OAc)4 binuclear complex (L is 4-(2-pyridyl)benzothiazole) were determined by X-ray diffraction analysis. The copper atoms have a distorted tetragonal bipyramidal environment and are coordinated to the nitrogen atom of the pyridine moiety of the ligand and to two oxygen atoms of the bridging acetate ligands. The Cu-Cu distance is 2.6129(9) Å. The electrochemical behavior of the synthesized ligands and complexes was studied using the cyclic voltammetry and rotating disk electrode techniques in DMF solutions (0.1 M Bu4NClO4). The primary reduction of all the complexes under study is directed to the metal. 相似文献
5.
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
6.
E. V. Tretyakov S. V. Fokin G. V. Romanenko V. N. Ikorskii A. V. Podoplelov V. I. Ovcharenko 《Russian Chemical Bulletin》2006,55(1):66-73
An efficient procedure was developed for the synthesis of alkyltetrazolyl-substituted nitronyl nitroxides (L
1 and L
2). These compounds were used to prepare the first alkyltetrazolyl-substituted imino nitroxides (L
3 and L
4). The molecular structures of L
3 and L
4 were confirmed by X-ray diffraction. Investigation of the products prepared by the reaction of copper(II) bis(hexafluoroacetylacetonate), Cu(hfac)2, with nitroxides made it possible to divide ligands L
1—L
4 into two groups. The reactions of spin-labeled tetrazoles L
1—L
3 with Cu(hfac)2 afford the heterospin complexes Cu(hfac)2L2, whereas L
4 serves as a bidentate ligand in the Cu(hfac)2
L
4 complex. In the solid Cu(hfac)2L2 complexes, antiferromagnetic exchange interactions between the unpaired electrons of the nitroxide fragments of the adjacent
molecules prevail, due to which μeff decreases with decreasing temperature, and the spins of nitroxides are completely compensated at 5–10 K. The Cu(hfac)2
L
4 complex displays strong intramolecular ferromagnetic coupling, due to which μeff at room temperature is close to 2.9 μB.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 64–70, January, 2006. 相似文献
7.
V. I. Ovcharenko S. V. Fokin G. V. Romanenko V. N. Ikorskii R. Z. Sagdeev D. S. Yachevskii D. L. Chizhov V. N. Charushin 《Russian Chemical Bulletin》2006,55(11):1904-1908
Heterospin complexes of bis(μ2-1,1,2,2,8,8,9,9-octafluorononane-3,5,7-trionato)dicopper(II) ([Cu2L2]) with nitronyl nitroxides 2-(1-methyl-1H-pyrazol-4-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-1-oxyl 3-oxide (2) and 4,4,5,5-tetramethyl-2-(3-pyridinyl)-4,5-dihydro-1H-imidazole-1-oxyl 3-oxide (1) were synthesized and structurally characterized. Crystals of the complexes are formed by the discrete bis[1-methyl-4-(4,4,5,5-tetramethyl-3-oxide-1-oxyl-4,5-dihydro-1H-imidazol-2-yl)-1H-pyrazole]-bis (μ2-1,1,2,2,8,8,9,9-octafluorononane-3,5,7-trionato)dicopper(II) etherate (3) and bis[3-(4,4,5,5-tetramethyl-3-oxide-1-oxyl-4,5-dihydro-1H-imidazol-2-yl)pyridine]-bis (μ2-1,1,2,2,8,8,9,9-octafluorononane-3,5,7-trionato)dicopper(II) (4) molecules. Each Cu atom of the dinuclear chelate fragment coordinates one paramagnetic ligand through the N atom of the
pyrazole or pyridine fragment, respectively. In complex 3, the paramagnetic ligands are located on one side of the plane of the chelate fragment, whereas the ligands in complex 4 are located above and below the plane of the chelate fragment. The magnetic properties of complexes 3 and 4 are determined by dominant antiferromagnetic exchange interactions between the unpaired electrons of the CuII atoms in the dinuclear Cu2L2 moiety.
Dedicated to Academician O. M. Nefedov on the occasion of his 75th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1836–1840, November, 2006. 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.
K. L. Tokarev M. A. Kiskin A. A. Sidorov G. G. Aleksandrov V. N. Ikorskii I. P. Suzdalev V. M. Novotortsev I. L. Eremenko 《Russian Chemical Bulletin》2008,57(6):1209-1214
The mononuclear complexes (η3-terpy)M(Piv)2·MeCN (M = Fe
ii
(3) and Co
ii
(4), and Piv is the pivalate anion) were synthesized by the reactions of polymeric iron(ii) and cobalt(ii) pivalates with 2,2′:6′,2″-terpyridine (terpy). The oxidation of compound 3 affords the pentanuclear heterospin iron(ii,iii) complex (η3-terpy)Fe5(μ4-O)(μ3-OH)(μ-OH)2(μ-Piv)7(η1-Piv)2 (5). All compounds were characterized by X-ray diffraction.
Dedicated to the 90th anniversary of the L. Ya. Karpov Institute of Physical Chemistry.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1186–1190, June, 2008. 相似文献
10.
T. V. Mitkina D. Yu. Naumov O. A. Gerasko F. M. Dolgushin C. Vicent R Llusar M. N. Sokolov V. P. Fedin 《Russian Chemical Bulletin》2004,53(11):2519-2524
The inclusion compound of macrocyclic cavitand cucurbit[8]uril (CB[8]) with the nickel(II) complex containing the tetraazamacrocyclic ligand cyclam, {[Ni(cyclam)]@CB[8]}Cl2··16H2O (1), and the inclusion compounds of CB[8] with the copper(II) bis-ethylene-diamine complex, {trans-[Cu(en)2(H2O)2]@CB[8]}Cl2·{CB[8]}·42H2O (2a) and {trans-[Cu(en)2(H2O)2]@CB[8]}Cl2·17H2O (2b), were synthesized and characterized by X-ray diffraction analysis, IR and ESR spectroscopy, and electrospray mass spectrometry. Guest—host inclusion compounds can be directly synthesized starting from a metal complex and cucurbit[8]uril, as was exemplified by the preparation of compounds 2a and 2b.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2414–2419, November, 2004. 相似文献
11.
V. A. Livshits A. M. Pronin V. V. Samoshin S. P. Gromov M. V. Alfimov 《Russian Chemical Bulletin》1994,43(11):1827-1833
Six copper(ii) chloride complexes with crown ethers containing besides oxygen also nitrogen or sulfur atoms in 15- or 18-membered cycle were studied by ESR and electron absorption spectroscopies. Theg and HFI tensor components determined by spectral simulation indicate rhombic symmetry and localization of an unpaired electron on the d
xy
orbital for all the complexes. The unpaired electron fractions on - and -type metal ion and ligand AO were estimated from ESR and absorption spectra using LCAO MO method. Both - and -type bond covalences were shown to be greater in these complexes compared to only oxygen-containing crown ether complexes. The temperature dependence of g and A components in some complexes may be due to conformational changes.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1938–1944, November, 1994.The present work was carried out with financial support from the Russian Foundation for Basic Research (Project 93-03 04089). 相似文献
12.
S. Yu. Troitskii A. L. Chuvilin D. I. Kochubei B. N. Novgorodov V. N. Kolomiichuk V. A. Likholobov 《Russian Chemical Bulletin》1995,44(10):1822-1826
The structure of polynuclear PdII hydroxocomplexes (PHC) formed as a result of alkaline hydrolysis of PdII chloride complexes was studied by EXAFS, SAXS, and TEM methods. It is established that in aqueous solutions a hydroxocomplex particle is a filament curled into a ball containing about 100 Pd atoms. The filament consists of planar coordination squares of PdO4 units linkedvia one or two oxygen bridges of different geometry. Aging of samples results in an increase in the number of single bridging ligands and a decrease in the diameter of particles. Interatomic distances around palladium atoms were determined.Translated fromIzvestiya Akademii Nauk. Seriya Khimlcheskaya, No. 10, pp. 1901–1905, October, 1995. 相似文献
13.
E. K. Beloglazkina I. V. Yudin A. G. Majouga A. A. Moiseeva A. I. Tursina N. V. Zyk 《Russian Chemical Bulletin》2006,55(10):1803-1809
The reactions of 2-(2-pyridyl)benzothiazole (1) with MX2·nH2O salts (M = NiII, CoII, or CuII; X = Cl or ClO4; n = 0–2) in EtOH afforded the corresponding complexes. Depending on the nature of the counterion in the starting metal salt,
the reactions give compounds of composition M(1)Cl2·nH2O or Cu(1)2(ClO4)2·H2O. The molecular and crystal structure of the CuII(1)2(ClO4)2·H2O complex was established by X-ray diffraction. The copper atom in this complex has a distorted tetragonal-pyramidal ligand
environment and is coordinated by four nitrogen atoms of two ligand molecules and one water molecule. Electrochemical study
of the ligand and the resulting complexes by cyclic voltammetry and at a rotating disk electrode demonstrated that ligand
1 stabilizes reduced forms of complexes containing Ni, Co, or Cu atoms in the oxidation state +1.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1738–1744, October, 2006. 相似文献
14.
Y. Z. Voloshin I. S. Makarov A. V. Vologzhanina E. V. Polshin Yu. B. Monakov R. M. Islamova Yu. N. Bubnov 《Russian Chemical Bulletin》2008,57(6):1215-1222
The direct template macrocyclization of 2,3-butanedione monooxime hydrazone (HDXO) with ferrocenylboronic acid on the iron(ii) ion matrix afforded the ferrocenylboron-capped semiclathrochelate iron(ii) oximehydrazonate. The H+ ion-catalyzed macrocyclization of this precursor with an excess of triethyl orthoformate gave the clathrochelate complex with syn,syn,syn-orientation of the ethoxy substituents relative to the 1,3,5-triazacyclohexane ring. The complexes synthesized were characterized using elemental analysis, IR and UV—Vis spectroscopies, MALDI-TOF mass spectrometry, 1H and 13C{1H} NMR, 57Fe Mössbauer spectroscopies, and X-ray diffraction analysis. 相似文献
15.
S. V. Korenev D. B. Vasil’chenko I. A. Baidina E. Yu. Filatov A. B. Venediktov 《Russian Chemical Bulletin》2008,57(8):1637-1643
The complex salts [Rh(γ-Pic)4Cl2]X, where X = Cl, ReO4, or ClO4, were synthesized and characterized by IR spectroscopy, elemental analysis, X-ray powder diffraction, and single-crystal
X-ray diffraction. The salts containing the ReO4
− and ClO4
− ions are isostructural. The oxidation of the γ-picoline complexes afforded a complex with isonicotinic acid. The crystalline
product of the oxidation reaction was isolated and characterized by X-ray diffraction. The crystal structure contains two
types of rhodium complex cations, which differ in the number of oxidized γ-picoline molecules. Thermal transformations of
the complexes were studied by DTA, as well as by DTA coupled with evolved gas analysis. The thermolysis products were isolated
and studied by IR and NMR spectroscopy.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1607–1613, August, 2008. 相似文献
16.
The addition of the macrocyclic polyether 18-Crown-6 (18C6) increases the selectivity of oxidation of ethylbenzene to -phenylethylhydroperoxide (PEH) in the presence of Ni(acac)2. The initial oxidation rate, selectivity and degree of conversion of ethylbenzene to PEH are greater than those catalyzed by Ni(acac)2 only. The efficiency of the macrocyclic ligand as an activator of Ni(acac)2 exceeds that of monodentate donor ligands. The high selectivity of the process is due to both the primary Ni(acac)2 · 18C6 complexes and the products of their transformation in the course of oxidation. The mechanism of ethylbenzene oxidation catalyzed by Ni(acac)2 · 18C6 complexes is discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1406–1411, August, 1994. 相似文献
17.
V. V. Potekhin 《Russian Chemical Bulletin》2007,56(5):875-882
The oxidation of lower aliphatic alcohols C1–C4 with dioxygen to form the corresponding carbonyl compounds in the presence of the PdII tetraaqua complexes and FeII-FeIII aqua ions in an aqueous medium was studied at 40–80 °C. The introduction of an aromatic compound (acetophenone, benzonitrile,
phenylacetonitrile, o-cyanotoluene, nitrobenzene) and FeII aqua ion instead of the FeIII aqua ion into the reaction system increases substantially the catalytic activity and the yield of the carbonyl compound.
The key role of the Pd species in the intermediate oxidation state stabilized by the aromatic additive in the catalytic cycle
of alcohol oxidation with dioxygen to the carbonyl compound was shown. An increase in the kinetic isotope effect with an increase
in the temperature of methanol oxidation indicates a change in the rate-determining step of alcohol oxidation with dioxygen
in the presence of PdII-FeII-FeIII and the aromatic compound. At temperatures below 60 °C, the catalytically active palladium species are mainly formed upon
the reduction of the PdII tetraaqua complex with the FeII aqua ion, whereas at higher temperatures the reaction between the alcohol and PdII predominates. The mechanism and kinetic equation of the process were proposed.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 842–848, May, 2007. 相似文献
18.
E. K. Beloglazkina A. V. Shimorsky A. G. Majouga A. A. Moiseeva N. V. Zyk 《Russian Chemical Bulletin》2007,56(11):2189-2199
Transition metal complexes (NiII, CoII, and CuII) with tetradentate N2S2-type ligands (L), which are reaction products of 2-thio-substituted benzaldehydes with aromatic amines (3-aminopyridine or
2-aminothiophenol), were synthesized for the first time. The complexes have the composition L·MX2 or L·2MX2 (X = Cl or ClO4). The electrochemical behavior of the ligands and complexes was studied by cyclic voltammetry and rotating disk electrode
voltammetry. Depending on the structure of the complexes, the metal atom in the latter is initially reduced in a one-or two-electron
process.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2115–2124, November, 2007. 相似文献
19.
V. N. Leibzon L. V. Michalchenko M. Yu. Leonova V. P. Gultyai 《Russian Chemical Bulletin》2005,54(5):1203-1207
Small additives of iron(II) or copper(II) salts change the regioselectivity of 2,4,6-trinitrotoluene monoreduction with titanium(III) chloride affording predominantly less accessible 2-amino-4,6-dinitrotoluene over 4-amino-2,6-dinitrotoluene (from 25% when
the reduction occurs in the absence of the iron and copper salts to 70% in the presence of these salts). A possible mechanism
of the process is discussed.
Dedicated to Academician N. K. Kochetkov on the occasion of his 90th birthday.
__________
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1172–1176, May, 2005. 相似文献
20.
N. V. Zyk E. K. Beloglazkina S. E. Sosonyuk M. N. Bulanov R. L. Antipin 《Russian Chemical Bulletin》2005,54(6):1488-1491
Electrophilic sulfenylation, selenenation, and halogenation of bicyclo[2.2.1]heptenes containing CF3 or NO2 group in position endo-5 were studied. The sulfenylation and selenenation were accomplished by arylsulfene- and arylselenenamides activated by POHal3 (Hal = Br, Cl), and iodination was performed by KICl2. The reactions are regiospecific and involve an exo-attack of the electrophilic fragment (arylthio or arylseleno group or iodine) on the C=C bond atom located closer to the
CF3 or NO2 group.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1445–1448, June, 2005. 相似文献