научный журнал по химии Координационная химия ISSN: 0132-344X

БУШУК Б.А., БУШУК С.Б., ГРИГОРЬЕВ И.С., ДУГЛАС В.Е., КАЛЬВИНКОВСКАЯ Ю.А., КЛАПШИНА Л.Г., КУЗНЕЦОВА О.В., ЛОПАТИН М.А., СЕМЕНОВ В.В., ЧЕРЕПЕННИКОВА Н.Ф. — 2007 г.

3-(3-Триэтоксисилилпропил)пентан-2,4-дион, (EtO)3SiCH2CH2CH2C[ C(O)CH3]2 (I), синтезирован из 3-аллилпентан-2,4-диона, CH2 = CH CH2 C[ C(O)CH3]2, и триэтоксисилана, (EtO)3SiH, в присутствии катализатора Спайера. Силилирование протекает преимущественно по концевому атому углерода аллильной группы. -Дикетонатные комплексы европия(III), тербия(III) и иттербия(III) синтезированы из соединения I и соответствующих изопропилатов РЗМ. На их основе сформированы прозрачные золь–гель пленки, содержащие катионы Eu3+, Tb3+ и Yb3+. Процесс образования пленок исследован методом ИК-спектроскопии. Показано, что под действием влаги происходит не только гидролиз и конденсация триэтоксисилильных групп, но также гидратация катиона РЗМ. В случае комплекса тербия при возбуждении в одну из двух полос (230 и 308 нм), имеющихся в спектре возбуждения флуоресценции, наблюдается интенсивная флуоресценция катиона: четыре узкие полосы переходов 5D4 7F6 (491 нм), 5D4 7F5 (547 нм), 5D4 7F4 (585 нм), 5D4 7F3 (623 нм), из которых наиболее интенсивным является переход 5D4 7F5. При этом эмиссия кремнийорганической матрицы в области 440 нм не проявляется. Для пленок, содержащих катионы Eu3+, получены спектры испускания, содержащие наряду с эмиссией от катиона при 593, 618, 667, 700 нм (переходы 5D0 7F1, 5D0 7F2, 5D0 7F3, 5D0 7F4) интенсивную полосу при 491 нм от матрицы.

БЕЛЯЕВ А.Н., ГОРЛОВ М.Ю., ЕРЕМИН А.В., ПАНИНА Н.С., СИМАНОВА С.А., ФИШЕР А.И. — 2007 г.

При действии диметилсульфоксида (DMSO) на в растворе метанола получены два сольвата – [Ru3O(O2CCF3)6(DMSO)3] · 1/2H2O (I) и [Ru3O(O2CCF3)6(DMSO)3] · H2O (II) – нового трехъядерного смешановалентного трифторацетатного комплекса рутения(II, III, III), в котором две молекулы DMSO координированы к атомам рутения через атомы кислорода, а третья – через атом серы. По данным РСА, комплекс может кристаллизоваться в двух сингониях: триклинной (I) (пр. гр. P ) и моноклинной (II) (пр. гр. P21/m). Параметры элементарной ячейки для I: a = 9.354, b = 11.005, c = 20.846 A, = 99.10, = 96.38, = 92.17, Z = 2; R = 7.27%; для II: a = 9.186, b = 17.044, c = 13.091 A, = 101.10, Z = 2; R = 14.18%.

AQRA F. M. A. M., JAMHOUR R. M. A. Q. — 2007 г.

CHEN S.P., L GAO S., SHI Q.Z., YANG X.W. — 2007 г.

Thirteen solid ternary complexes of Ln(Pdc)3(Phen) (Ln = La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) have been synthesized in absolute ethanol by rare-earth element chloride low hydrate reacting with the mixed ligands of ammonium pyrrolidinedithiocarbamate (APdc) and 1,10-phenanthroline · H2O (o-Phen · H2O) in the ordinary laboratory atmosphere without any cautions against moisture or air sensitivity. IR spectra of the complexes showed that the Ln3+ coordinated with six sulfur atoms of three Pdc– and two nitrogen atoms of o-Phen · H2O. It is assumed that the coordination number of Ln3+ is eight. The constant-volume combustion energies of the complexes, cU, were determined by a precise rotate-bomb calorimeter at 298.15 K. Their standard molar enthalpies of combustion, , and standard molar enthalpies of formation, were calculated.

ALI S., SHAHID K., SHAHZADI S. — 2007 г.

The complexes of two organic carboxylates (containing {O,O}-donor atoms) with Me2Sn(IV)Cl2, n-Bu2Sn(IV)Cl2, Bz2Sn(IV)Cl2, Oct2Sn(IV)O, Me3Sn(IV)Cl, n-Bu3Sn(IV)Cl, Ph3Sn(IV)Cl, and Bz3Sn(IV)Cl having ligand-to-metal ratios of 1 : 2 and 1 : 1 were prepared by two different methods. The FT-IR spectra clearly demonstrated that organotin(IV) moieties react with {O,O}-atoms of the ligands. It was found that in all cases the COO- group was acting as bidentate in the solid state. The 119Sn NMR data revealed that the organotin(IV) moiety has a tetrahedral geometry in non-coordinating solvents. The biological activity of these compounds was compared with that of their precursors, and all the synthesized compounds show significant antibacterial activity. The antifungal activity of the complexes against six plant pathogens has been estimated. The complexes display marked toxicity against these fungi and are more fungitoxic than free acids. The compounds have also shown significant cytotoxicity against Brine Shrimp (Artemia salina).

FAHMI N., GARG R., SINGH R.V. — 2007 г.

The Schiff bases, 3-(indolin-2-one)hydrazinecarbothioamide (L1H), 3-(indolin-2-one)hydrazinecarboxamide (L2H), 5,6-dimethyl-3-(indolin-2-one)hydrazinecarbothioamide (L3H), and 5,6-dimethyl-3-(indolin-2-one)hydrazinecarboxamide (L4H), have been synthesized by the condensation of lH-indol-2,3-dione and 5,6-dimethyl-lH-indol-2,3-dione with the corresponding hydrazinecarbothioamide and hydrazinecarboxamide, respectively. The complexes of oxovanadium and ligands have been characterized by elemental analyses, melting points, conductance measurements, molecular weight determinations, and IR, 1H NMR and UV spectral studies. These studies showed that the ligands coordinated to the oxovanadium in a monobasic bidentate fashion through oxygen or sulfur and the nitrogen donor system. Thus, penta- and hexacoordinated environment around the vanadium atom has been proposed. All the complexes and their parent organic moieties have been screened for their biological activity on several pathogenic fungi and bacteria and were found to possess appreciable fungicidal and bactericidal properties.

KUMAR R., SINGH S. — 2007 г.

Two novel macrocyclic ligands and their complexes Mn(L1 and L2)]X2 (L1 and L2 = 1,10-diaza-5,6,15,17-tetraoxa (tetrathia)-2,3:8,9:12,13,18:19-tetrabenzocyclododeca-10,20-diene; X = Cl, NO3, NCS, SO4) were primed and their capacity to sustain the Mn2+ ion in solid, as well as in aqueous solution, was resoluted from an assortment of physicochemical measurements, viz., elemental analyses, molar conductance measurements, magnetic susceptibility measurements, mass, IR, 1H NMR electronic, ESR spectral studies, and cyclic voltammetric (CV) measurements.

DUAN L.Y., GAO E.J., LIU Q.T. — 2007 г.

A mixed-ligand complex [Pd(Phen)(Phe)]Cl · H2O (Phen – o-phenantroline, Phe – L-phenylalanine) is synthesized and structurally characterized by elemental analyses and single-crystal X-ray diffraction. Diffraction data: C21H19ClN3O3Pd, monoclinic, P21/n, a = 9.478(4), b = 22.395(9), c = 9.528 (4) A, = 104.358(11)°, V = = 1959.3(14) A3, Z = 4. The Pd atom has planar-square coordination geometry and is surrounded by the Phen and Phe ligand to form a monovalent complex cation, Cl– is filled in the crystal lattice asa counterion. The Cl atom connects the complex cation through an electrostatic interaction and has a very weak hydrogen bond with a water molecule. Hydrogen bonding interactions and stacking interactions stabilize the crystal lattice. The anticancer activity of the complex increases with the increasing concentration of the complex, which shows that the complex has strong anticancer activity.

КОЖОМУРАТОВА Ж.С., НАУМОВ Д.Ю., НАУМОВ Н.Г., УСКОВ Е.М., ФЕДОРОВ В.Е. — 2007 г.

Взаимодействием расплава трибензиламина с кластерными соединениями молибдена, Mo6Cl12 и (H3O)2Mo6Cl14 · 6H2O, получены соли (Bz3NH)3[Mo6OCl13] (I) и (Bz3NH)2[Mo6Cl14] · 2CH3CN (II). Соединение II содержит известный кластерный анионный комплекс [Mo6Cl14]2. Соединение I содержит новый кластерный анионный комплекс [Mo6OCl13]3, в котором один внутренний атом хлора замещен на атом кислорода. Комплекс II демонстрирует фосфоресцентное свечение в длинноволновой области видимого спектра.

AHMAD F., ALI S., ASHRAF R., BHATTI M.H., SHAHZADI S., YAQUB S. — 2007 г.

Different vanadium(IV) complexes of general formula VF2L2 have been synthesized, where L are various nonsteroidal antiinflammatory drugs. The complexes are characterized by elemental analysis, UV-visible, and infrared spectroscopy. The metal contents estimated by the ICP-AES method in the synthesized complexes are in good agreement with their calculated values and spectroscopic data proposed the octahedral geometry for the reported complexes. Conductance measurements show the nonelectrolytic nature of complexes. Biological screening tests against different bacteria and fungi show significant antibacterial and antifungal activity for all the complexes.

KIZILCIKLI I., KURT Y.D., POZAN G.S., ULKUSEVEN B. — 2007 г.

Mixed ligand complexes of dioxomolybdenum(VI) with 2-hydroxybenzaldehyde 4-phenyl-S-methylthiosemicarbazone (H2L) were prepared with the formula [MoO2(L)D] (D = H2O; methyl, n-butyl, and n-undecyl alcohol; DMF, DMSO, pyridine, 4-picoline, and 3,5-lutidine). The compounds were characterized by elemental analysis, IR and 1H NMR spectroscopy. The thermal decomposition of the compounds were investigated by using TGA, DTG, and DTA methods in air, and the thermal behavior depending on the second ligand molecule was discussed. A single crystal of the DMF coordinated complex was studied by X-ray diffractometry.

KALSOTRA B.L., PATHANIA M.S., SHEIKH H.N. — 2007 г.

GRAY H.B., KAUFFMAN G.B., KAUFFMAN L.M. — 2007 г.

BO Q.B., CHEN C.L., LI Y.X., SHENG Y.L., SUN G.X., SUN Z.X., ZHANG Z.W., ZHAO S.Y. — 2007 г.

Hydrothermal synthesis, characterization (IR, TG/DTA, element analysis, inductively coupled plasma (ICP)) and single-crystal X-ray structures of H4Btec hydrate and its two cobalt complexes, colorless [H4Btec · 2H2O]n (I), pink [Co(H2O)6(H2Btec)]n (II), and nacarat {[Co(H2O)3(H2Btec)(Phen)] · H2O}n (III) (H4Btec = 1,2,4,5-benzenetetracarboxylic acid, Phen = 1,10-phenanthroline) have been solved. The results showed that I forms a 3D O–H···O hydrogen-bonded network generated from H4Btec and water molecules, II presents a 3D network constructed by mononuclear [Co(H2O)6]2+ cations and H2Btec2 dianions through extensive hydrogen-bonding interactions, and III gives rise to a pseudo-octahedral coordination geometry. Extensive hydrogen-bonding interactions have significant effects in configuring a 3D network constructed by mononuclear [Co(H2Btec)(Phen)(H2O)3] neutral molecules and a water molecules.

BYABARTTA P., LAGUNA M. — 2007 г.

The reaction of [Au(OSO2CF3)(PPh3)] with arylazoimidazole in dichloromethane followed by NH4PF6 leads to [Au(RAaiR’)(PPh3)]PF6 (RAaiR = p-R N = N C3H2 NN 1 R), abbreviated as N,N/-chelator, where N (imidazole) and N (azo) represent N and N, respectively; R = H (a), Me (b), Cl (c), and R = Me (I), CH2CH3 (II), CH2Ph (III)]. IR spectra of the complexes show –C=N– and –N=N-stretchings at 1590 and 1370 and at 1100, 755, 695, 545, and 505 cm-1 due to the presence of the triphenylphosphine ring. The 1H NMR spectral measurements suggest that methylene ( CH2 ) in (RAai)Et gives a complex of the AB type multiplet with a coupling constant of 7.6 Hz while in RAaiCH2Ph it shows AB type quartets with coupling constant of av. 7.2 Hz. Considering the arylazoimidazole moity, there are different carbon atoms in the molecule giving different peaks in the 13C NMR spectrum of the complexes. In the 1H 1H COSY spectrum of the present complexes, the absence of any off-diagonal peaks extending from = 14.12 and 9.55 ppm confirms their assignment of no proton on N(1) and N(3), respectively. Contour peaks in the 1H 13C HMQC spectrum in the present complexes, the absence of any contours at = 157.12, 160.76, 155.67, and 157.68–160.2 ppm assign them to the C(2), C(6), C(12), and C(PPh3) carbon atoms, respectively. The solution structure and stereoretentive transformation in each step have been established from the 1H NMR results.

PANDEY O.P., SENGUPTA S.K., TRIPATHI S. — 2007 г.

Lanthanum(III) and praseodymium(III) complexes of the type [Ln(L)Cl(H2O)]2 (Ln = La(III) or Pr(III); LH2 = = dithiosemicarbazone ligands derived from piperazine dithiosemicarbazide and benzaldehyde, 4-nitrobenzaldehyde, and 2-methoxybenzaldehyde) have been synthesized in methanol in the presence of sodium hydroxide. The complexes have been characterized by elemental analyses, molecular weight, molar conductance, electronic absorption, IR, and 1H and 13C NMR spectral studies. Nephelauxetic ratio, covalency parameter, and bonding parameter for these complexes have also been calculated. Thermal studies of the complexes have been carried out using TG, DTG, and DSC techniques. Kinetic parameters, such as apparent activation energy and order of reaction, were determined by the Coats–Redfern graphical method. The heats of reaction for different reaction steps were calculated from DSC curves.

JOSEPH J., RAJA J.D., RAJA S.J., RAMAN N. — 2007 г.

Three novel oxovanadium(IV) Schiff base complexes, [VO(Phen)(L)]SO4, where L = 4[(benzylidene)amino]antipyrine (Ia), 4[(cinnamalidene)amino]antipyrine (Ib) and 4[(2-chlorobenzylidene)amino]antipyrine (Ic) are designed using benzaldehyde/cinnamaldehyde/2-chlorobenzaldehyde with 4-aminoantipyrine, 1,10-phenonthroline, and vanadyl sulfate in the 1 : 1 : 1 molar ratio. They are synthesized by the template method. The geometry of the complexes is elucidated by elemental analyses, IR, UV-Vis, ESR, CV, FAB mass, magnetic susceptibility, and conductance data. FAB mass shows the degradation of the complexes. The electronic spectra of the complexes indicate that the complexes have square pyramidal geometry in which the ligands act as tetradentate. Their electrochemical parameters, the anodic and cathodic potentials, and the number of transferred electrons are calculated. One quasi-reversible peak and one electron-transfer redox processes corresponding to the formation of a VO(II)/VO(III) couple are observed. The antimicrobial activity of synthesized complexes is tested. The results are compared with the standard penicillin. DNA cleavage experiments showed that Ia exhibits higher cleavage efficiency, whereas Ib and Ic have the lower cleavage efficiency.

DEVECI P., OZCAN E., YILDIRIM B. — 2007 г.

Two new vic-dioxime ligands and their complexes with Co+2, Ni+2, Cu+2, Cd+2, and Zn+2 ions were synthesized. Primer amines (3,4-methylenedioxaaniline and 4-methylbenzylamine) reacted with antichloroglyoxime to give 3,4-methylenedioxaphenylaminoglyoxime (H2L1) and N-(4-methylbenzyl)aminoglyoxime (H2L2) ligands. Structures of the ligands and their complexes are proposed based on elemental analyses, IR, UV-Vis, and 1H NMR spectra, magnetic susceptibility measurements, and thermogravimetric analyses (TGA).

ERCAG A., KARAHAN S., SUBASI E. — 2007 г.

New complexes cis-[M(CO)4-DABRd] (M = Cr (I), Mo (II) and fac-[M(CO)3-SAT] (M = Cr (III), Mo (IV)) have been synthesized by the photochemical reactions of cis-[( 4-NBD)M(CO)4] (NBD is norbornadiene; M = = Cr, Mo) with 5-(4-dimethylaminobenzylidene) rhodanine (DABRd) and salicylidene-3-amino-1,2,4-triazole (SAT) ligands and characterized by elemental analysis, FT-IR and 1H NMR spectroscopy, and mass spectrometry. The spectroscopic studies show that the DABRd ligand acts as a bidentate ligand coordinating via both NH–(S)C=S sulfur donor atoms in I and II and SAT ligand behaves as a tridentate ligand coordinating via its all imine nitrogen –C=N– donor atoms in III and IV to the metal center.

REN N., XU S.L., ZHANG H.Y., ZHANG J.J. — 2007 г.

1,10-Phenanthroline-tris(4-methoxybenzoate)dysprosium, Dy(p-MOBA)3Phen (where p-MOBA = p-methoxybenzoate and Phen = 1,10-phenanthroline), (I) has been synthesized. The complex was characterized by various techniques including elemental analysis, UV, IR, XRD, molar conductance, and TG–DTG. The crystals consist of binuclear molecules and monoclinic, space group P21/n: a = 14.143(6), b = 17.550(7), c = 14.493(6) A, = 117.357(4)°, Z = 2, c = 1.655 g сm-3, F(000) = 1588; R1 = 0.0176, wR2 = 0.0455. In the complex, each Dy3+ ion is nine-coordinate to one 1,10-phenanthroline molecule, one bidentate chelating carboxylate group, and four bridging carboxylate groups in which the carboxylate groups are bonded to the Dy3+ ions in three modes: bridging bidentate, bridging tridentate, and chelating bidentate. The thermal decomposition mechanism of I has been determined on the basis of thermal analysis. In addition, the lifetime equation at a weight-loss of 10% was deduced as ln = –28.8361 + 19478.37/T by isothermal thermogravimetric analysis.