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A slight structural modification while going from a 4,5-diazafluorene ligand to a 4,5-diazafluorene-9-one ligand leads to a significant change in the emission properties of their Zn(ii) and Cd(ii) complexes.

Based on a Bruker MSL-300 nuclear magnetic resonance (NMR) spectrometer, a method has been developed for upgrading the CXP, MSL, and Avance-I series spectrometers by converting them to a modern digital base and replacing analog signal processing with digital processing while preserving the standard radio-frequency (RF) components as much as possible. The upgrade means retaining the 250-W wide-band amplifier, the RF synthesizer with a frequency band of 0–250 MHz, and the narrow-band preamplifier with the complete elimination of an Aspect computer and the standard DISMSL control program. Outdated units for generating RF pulses and registering signals were modified. This enables to significantly improve the maintainability and reliability of the spectrometer and ensure its connection to a modern computer. Comparative measurements of the signal-to-noise ratio for Cu2O samples on 63Cu nuclei revealed a 1.5-fold increase in the sensitivity of the new scheme compared to the original Bruker MSL-300 NMR spectrometer.

Reactions of chiral nopinane-annulated diazafluorenone with substituted phenols and naphthols by the action of trifluoromethanesulfonic acid led to spiro products. The structure of the resorcinol derivative was confirmed by X-ray structural analysis.

Conifer essential oils have been used for centuries in traditional medicine, and nowadays they are of special interest for official medicine, aromatherapy and perfumery. In the present work, comprehensive information is given on the composition of essential oils prepared from the twigs of the conifer trees of the pine family (Pinaceae): Abies sibirica Ledeb., Larix sibirica Ledeb., Picea obovata Ledeb., Pinus sibirica Du Tour, Pinus sylvestris L. A total of 50 samples of essential oils have been studied. The samples were prepared during vegetation stage in the time period 1998-2012 from the growing wild trees in the South part of the Western Siberia (Russian Federation) and neighboring territories of Republic of Kazakhstan within the area with geographical coordinates LAT 49.180012-57.908583 and LON 83.213217-91.258717 at elevation of 82-2070 m above sea level. All the essential oil samples were obtained from freshly collected plant raw material by steam distillation at atmospheric pressure in stainless steel apparatus, which had been specially designed for field research. All the chromatographic profiles were prepared from authentic samples whose voucher specimens are deposited at the Central Siberian Botanical Garden of the Siberian Branch of the Russian Academy of Sciences (NS). The following information for each sample is provided: (1) date and location of the plant raw material collecting, indicating administrative areas and the exact geographic coordinates; (2) yield of essential oil, (3) chemical composition of the essential oil sample based on GC/MS experiments using full mass-spectra (EI, 70 eV) and linear retention indices of the components, (4) results of GC-FID quantification based on internal standards and response factors, (5) enantiomeric composition of the main components based on GC×GC experiments using the 2nd column with cyclodextrin-based chiral selector, (6) GC profile of the high-boiling fractions indicating the characteristic sesquiterpenoids. Therefore, this study provides reliable information about the variability and true composition of the Siberian conifer oils, and the experimental data given can serve as reference chromatographic profiles of volatile substances to solve the problems of quality, authenticity and safety.

Complexes [Zn(L2)2Cl2], [Pd2(L2)2Cl4], and CuL2Cl, where L2 is (−)-camphor thiosemicarbazone, were synthesized. The structures of complexes [Zn(L2)2Cl2] and [Pd2(L2)2Cl4] were determined by X-ray diffraction. The crystal structure of complex [Zn(L2)2Cl2] contains mononuclear molecules with distorted tetrahedral {ZnCl2S2} coordination units and monodentate L2 ligands. Complex [Pd2(L2)2Cl4] has binuclear structure with Pd metal centers linked by L2 ligands via μ2-S atoms. Complex CuL2Cl, according to IR and NMR spectra contains S and Cl atoms in the coordination sphere of ion Cu+. Complexes [Pd(tsc)Cl2] and Zn(tsc)2Cl2 (where tsc is thiosemicarbazide) were also obtained to determine the influence of the terpene moiety on cytotoxic properties of these compounds. Mononuclear complex [Pd(tsc)Cl2] contains an NSCl2 planar square coordination polyhedron, and tsc is a bidentate chelate ligand. The effects of tsc, L2, and the complexes with tsc and L2 on viability of the MCF-7 cell line were investigated next. The results showed that tsc and L2 are nontoxic at the tested concentrations (1–50 μM). All the complexes exerted a significant dose-dependent cytotoxic effect, whereas complex CuL2Cl was found to have the lowest half-maximal inhibitory concentration (IC50).

Intermetallic compounds with semiconducting properties are rare, but they give rise to advanced materials for energy conversion and saving applications. Here, we present ReGa

Mononuclear zinc(ii) and cadmium(ii) complexes, ZnLCl2 (1), CdLCl2 (2), ZnL1Cl2·2H2O (3), and CdL1Cl2·2H2O (4), with chiral ligands containing a 2,2'-bipyridine moiety and natural terpene (+)-limonene (L) or (+)-3-carene (L1) moieties were synthesized. In these complexes the L and L1 ligands are shown to coordinate Zn2+ and Cd2+ ions through the 2,2'-bipyridine moiety. The acetamide group of the ligands interacts with M2+ ions by forming NM2+ and C[double bond, length as m-dash]OM2+ contacts and N-HCl hydrogen bonds with coordinated Cl- ions. In solutions the complexes have several conformers differing by the degree of the turn of the acetamide moiety relative to the ligand core and the type of its interaction with the coordination core. The ligands and complexes exhibit luminescence with the quantum yield increasing in the order: ligandcadmium(ii) complexzinc(ii) complex. The complexes 3 and 4 demostrate excitation wavelength independent single-channel fluorescence. As opposed to 3 and 4, the complexes 1 and 2 demonstrate excitation wavelength dependent emission with nanosecond and microsecond lifetimes of the excited states. According to our TD-DFT calculations, an interplay of ligand centered and halide to ligand transitions facilitates two deactivation channels in 1 and 2: S1-S0 and T1-S0.

Reaction of fused 4,5-diazafluorene–bis(nopinane) with tere-phthalaldehyde, benzophenone, ninhydrin or anthraquinone in THF in the presence of TiCl4 and pyridine results in a formation of new chiral condensation products, which exhibit solvatochromism and pleochroism. Crystal structure of the key products has been determined by X-ray crystallography, and unusual colour behavior has been explained by DFT calculations.

Three salts of perchlorinated sulfonium and ammonium derivatives of tetrabuthylammonium nonachloro-closo-decaborate, (n-Bu4N)2[2-B10Cl9-cyclo-S(CH2)4S-B10Cl9] (1), (n-Bu4N)[2-B10Cl9-cyclo-S(C2H4)2O] (2) and (n-Bu4N)[1-B10Cl9N(n-Pr3)] (3) are synthesized and characterized using IR, 11B, 1H, 13C NMR, X-Ray and 35Cl NQR-spectroscopy. The noncovalent interactions involving chlorine atoms were identified by 35Cl NQR spectra. The results were discussed in comparison with those of X-ray diffraction analysis which are based on measuring contacts shorter than the sum of van der Waals (vdW) radii of atoms. It has been found that the crystal lattice of 2 exhibits dynamic properties strongly different from those of 1 and 3. Whereas the 35Cl NQR spectra of the latters were extremely wide (up to 1200 kHz), the spectrum of 2 demonstrated a narrowing of almost an order of magnitude (up to 120 kHz) which indicated a significant weakening of the tendency for the formation of intermolecular bonds by chlorine atoms of this cluster.

5,7,8-Trifluoro-3,4-dihydro-2H-1,4-benzothiazine, corresponding 1-oxide and 1,1-dioxide, as well as some of their 4- and 6-substituted derivatives were prepared in 39–88% yields via the reaction of ammonia or primary aliphatic amines with (2-haloethyl)-2,3,5,6-tetrafluorophenyl sulfides, sulfoxides, or sulfones. Formation of the heterocyclic moiety was shown to proceed as a two-stage process starting from halogen replacement at the side chain followed by intramolecular aminodefluorination. The ratio of the reaction rates of the two processes depends on the nature of the reagent used. Chemical structures of the cyclization products were proved by precise analysis of the NMR spectra and by comparing the experimental NMR parameters with those calculated by an empirical additivity scheme and quantum chemistry methods (DFT).

ReGaGe2 is a new member of the family of intermetallic compounds with non-metallic properties. It displays highly localized covalent bonding patterns. Its electronic structure is governed by mixing of Re d orbitals with the s and p orbitals of Ga and Ge and features the Fermi level falling into the opened band gap, ensuring experimentally confirmed semiconducting properties.

A series of lanthanide(iii) complexes based on the new chiral ligand L, which contains 1,10-phenanthroline and (-)-menthol fragments, namely [LnL2(NO3)3] (Ln = Eu (1), Gd (2), Tb (3), Dy (4)), have been synthesized and structurally characterized. Complexes 1-4 are isostructural and crystallize in the non-centrosymmetric space group P41212. The mononuclear complexes comprise a 10-coordinate Ln3+ ion with two bidentate N,N-donor ligands (L) and three bidentate chelating nitrate groups. The magnetic properties of complexes 1-4 are determined mainly by the Ln3+ ions. In the case of complexes 3 and 4, significant anisotropy results in nonlinear field dependences of magnetization at low temperature. Complexes 1, 3 and 4 exhibit metal-centered red (Eu3+), green (Tb3+) and yellow (Dy3+) luminescence, respectively, whereas complex 2 displays blue ligand-based luminescence in the solid state at room temperature. The luminescence quantum yield for the solid samples increases in the order 4 < 2 ≈ 3 < 1. The europium(iii) complex shows long luminescence lifetimes (up to 1750 μs) and a very high quantum yield (φf = 0.87); these make this compound promising for application in sensing and optoelectronics.

Mononuclear and dinuclear zinc(II) and cadmium(II) complexes, [ZnLCl2] (1) and [Cd2L2Cl4] (2), with a chiral pentacyclic dihydrophenanthroline ligand L bearing a natural monoterpene (–)-α-pinene fragment were synthesized. DFT calculations of the specific rotation [α] and an NMR study show that the molecules of ligand L, complex 1 and the monomeric form of complex 2 exist in CDCl3 solutions with the P-helix conformation for the dihydrophenanthroline moiety. The dihydrophenanthroline fragments of L and mononuclear complex 1 also exists as a P-helix in the solid state, whereas the crystalline dinuclear complex 2 exists as an asymmetric dimer, [Cd2Cl4LPLM], where LP and LM are the ligand with P-helix and M-helix conformations of the dihydrophenanthroline fragment respectively. Full sets of photophysical parameters for L and complexes 1 and 2 have been determined. Compounds L, 1 and 2 display blue luminescence (λmax = 427, 405 and 415 nm in the solid state, respectively). The ligand L and complex 2 show moderate-to high quantum yields of 44% and 24%, respectively. The quantum yield for complex 1 is 6%. The emission lifetimes increase on going along the spectrum of luminescence, and in the deep red region, a rise of luminescence with times of 200–500 ps is observed. These processes can be explained by the migration of excitons and the capture of excitation by “defective” centers.

In this paper we present study of the magnetic structure of multiferroic series Bi1-yLayFeO3 (y = 0, 0.015, 0.03, 0.05 and 0.10) using nuclear magnetic resonance (NMR) at 4.2 K and Mossbauer spectroscopy at room temperature on 57Fe nuclei. We observed the presence of cycloid type spatial spin-modulated structure (SSMS) in the whole range of compositions. The study of the concentration dependence of the anharmonicity parameter m revealed that at the temperature of liquid helium in the composition region y = 0 – 0.10 as well as at room temperature for y = 0.03 the magnetic state of multiferroics is described by cycloid type SSMS with a positive effective uniaxial constant of magnetic anisotropy Κu > 0 (“easy axis” model). The study at room temperature in turn revealed that magnetic state of the multiferroics with y = 0 – 0.03 is described by cycloid type SSMS with a positive effective uniaxial constant of magnetic anisotropy Κu > 0 (“easy axis” model). In contrast, the magnetic state of multiferroics with y = 0.05 and 0.10 is described by a negative effective uniaxial constant of magnetic anisotropy Κu

Reaction of (+)-pinocarvone oxime with 2-morpholinocyclopent-2-enone and FeCl3·6H2O affords chiral C2-symmetric fused derivative of 4,5-diazafluorene, whose oxidation with SeO2 gives nopinane-annelated derivatives of 4,5-diaza-9Hfluoren- 9-one (C2-symmetry) and of 9,9’-bi-4,5-diazafluorenylidene (D2-symmetry). Structures of the compounds synthesized were proved by X-ray crystallography.

The complexes [Cu(HL)Cl] · 0.25H2O (I), [Cu(HL1)Cl] · 0.5H2O (II), [Ag(HL)] · 0.5H2O (III) were obtained; HL– and (HL1)– are the anions of the chiral N-substituted aminoacetic acid derivatives containing the natural monoterpenes (+)-3-carene and (–)-α-pinene, respectively. The µeff values for paramagnetic complexes I and II are 1.92 and 1.81 µB, respectively. Single crystals of the coordination 1D polymer [Cu(HL)Cl · 2H2O]n (IV) were grown. According to the X-ray diffraction data (CIF file CCDC No. 1035219), the crystal structure of complex IV is made up of the zigzag chains [Cu(HL)Cl]n and water molecules. The coordination polyhedron of the Cu atom is a distorted square pyramid (ClN2O2). The anion HL– acts as a chelating and bridging tetradentate ligand coordinated through the N atoms of the NH and NOH groups as well as through the O atoms of the COO–groups linking two adjacent Cu atoms together. The IR spectra of complexes I and II also provide evidence for the coordination of the functional COO–, NOH, and NH groups. In complex III, the coordination sphere of the Ag atom is made up of the O atoms of the COO–group. Complex III shows weak green photoluminescence (λmax = 530 nm).

The [ZnLCl2] (1) and Cd2L2Cl4 (2) complexes, where L is ethyl 2-methyl-5-(prop-1-en-2-yl)pyrido[2,3-a]phenazine-3-carboxylate, were synthesized. The complexes were characterized by elemental analyses, 1H and 13C NMR spectroscopy, and X-ray powder diffraction. Single crystals of 1 and [Cd2L2Cl4]·4CH2Cl2 (3) have been grown. The structure of 1 consists of mononuclear molecules, while the structure of 3 is built up of centrosymmetrical binuclear [Cd2L2Cl4] complex molecules and uncoordinated CH2Cl2 molecules. In 1 and 3, L acts as a bidentate chelating ligand. There is five-membered ZnN2C2 chelate cycle in the [ZnLCl2] molecule. There are two five-membered CdN2C2 chelate cycles and a Cd2Cl2 dinuclear unit in the molecule of [Cd2L2Cl4]. The coordination polyhedra are distorted tetrahedron Cl2N2 (in the structure 1) and distorted tetragonal pyramid Cl3N2 (in the structure of 3). According to IR-spectroscopic data, complex 2 is binuclear. Complexes 1 and 2 display bright luminescence in CHCl3 solutions (λmax = 477 and 475 nm, respectively) and in the solid state (λmax = 510 and 529 nm, respectively). The free L ligand shows weak luminescence intensity (λmax = 441 and 467 nm in CHCl3 and solid state, respectively).

Reaction of pinocarvone oxime with enamines and FeCl3 or CuCl2 resulted in annulation of nopinane carbon frame with pyridine and regioselective formation of chiral nopinane-annelated pyridines in 20–39% yields. Chemical structure of the pyridine derivatives were proved by precise NMR study.

(+)-3-Carene-, (S)-(–)-α-pinene- and (R)-(+)-limonene-derived α-nitroso chlorides on treatment with an excess of acetone cyanohydrin afford the corresponding α-cyano oximes, whose structure was solved by X-ray crystallography.

3-(2-Methoxyphenylamino)caran-4-one and 2-(2-methoxyphenylamino)pinan-3-one E-oximes obtained from appropriate natural terpenes were transformed into 1: 1 complexes with PdCl2. The structures of the complexes were examined by X-ray diffraction.

The optically active complexes [Zn(L)2Cl2] (I) and [Zn(L1)2Cl2] (II) (L and L1 are thiosemicar-bazones of (+)-camphor and (−)-carvone, respectively) were obtained. The crystal structures of L and complex I were determined by X-ray diffraction. The structure of L consists of hydrogen-bonded molecules united into chains. The crystal structure of complex I is built from mononuclear molecules. The coordination polyhedron of the Zn atom is a distorted tetrahedron Cl2S2. The molecule L functions as a monodentate ligand. According to data from IR spectroscopy, complex II is structurally similar to complex I.

We have studied the effect of the engineered nanomaterial Taunit, containing multiwalled carbon nanotubes (MWCNTs), on the growth of Onobrychis arenaria seedlings and investigated whether affected plants uptake and accumulate MWCNTs. We found that 100 μg/mL and 1000 μg/mL of Taunit stimulated the growth of roots and stems, and enhanced the peroxidase activity in these parts of plants. Microscopy studies showed the presence of MWCNTs in the root and leaf tissues of seedlings exposed to Taunit, suggesting that MWCNTs have a capacity to penetrate the cell walls, accumulate in roots and translocate to the leaves. Thus the stimulating effect of MWCNTs on seedlings of O. arenaria may be associated with the primary uptake and accumulation of MWCNTs by plant roots followed by translocation to the other plant tissues.

The complex of CdCl2 with 2-(3,5-dimethylpyrazol-1-yl)-4-methylquinoline (L), Cd2(L)Cl4 (I), is synthesized. According to the X-ray diffraction data, the structure of coordination polymer I is formed by chains in which two crystallographically independent Cd atoms linked by the bridging Cl atoms have different coordination numbers (5 and 6) and different environments. Five Cl atoms form the coordination polyhedron of the Cd(2) atom: a square pyramid (Cd-Cl 2.554(3)–2.689(3) A) completed to a bipyramid by the CI atom at a substantially longer distance of 2.865(4) A. Two Cl atoms and the N atom of quinoline fragment L are arranged in the equatorial plane of the coordination polyhedron of the Cd(1) atom, which is a distorted trigonal bipyramid. The axial vertices are occupied by the N atom of the pyrazole cycle of L and the Cl atom. Five-membered metallocycles CdCN3 are formed upon the coordination of bidentate chelating ligands L. The planes of L of two adjacent chains are parallel (the distances between them are ∼3.5 A), which suggests the π-π interaction between the planes. The luminescence excitation spectrum of compound I has a broad band with λmax = 350 nm. The spectrum of bright blue photoluminescence of compound I (300 K, λexc = 340 nm) contains an intense band with λmax = 420 nm.

Coordination compounds Cu2(H2L1)Cl4 (I), Pd2(H2L1)Cl4 (II), Cu2(H2L2)Cl4 (III), and Pd2(H2L2) Cl4 (IV) with chiral bis-α-sulfanyloximes, the derivatives of the monoterpenoid (−)-α-pinene, were obtained. The complexes I and III are paramagnetic (μeff = 2.45 and 2.67 μB, respectively), II and IV are diamagnetic. According to IR spectroscopy, in the compounds I–IV the nearest environment of Cu and Pd atoms includes N, S, and Cl atoms. The values of μeff and parameters of ESR spectra of the solid phase and solutions of I and III show a binuclear structure of the Cu(II) complexes. Parameters of the 1H and 13C NMR spectra of compounds II and IV indicate the formation of binuclear Pd(II) complexes of C2 symmetry and the closure of fivemembered chelate rings PdNSC2. The PdCl2 fragments are in transoid position. H2L1 and H2L2 are tetradentate bridging chelating ligands.

The Cu2LCl4 complex (I) with chiral bis{(E)-[(1S,4R)-Δ7,8-1-amino-2-para-menthalidene]aminohydroxy} methane (L — a derivative of natural monoterpenoid (R)-(+)-limonene) is synthesized. The crystal structure of the solvate of complex I[Cu(L)(μ-Cl)CuCl3] · iso-PrOH (II) is determined by X-ray diffraction analysis. Structure II is based on molecules of the [Cu(L)(μ-Cl)CuCl3] binuclear complexes in which L is the tetradentate cycleforming ligand. One Cl atom manifests the bridging function. The CuN4 Cl coordination unit is a square pyramid, and CuCl4 is a distorted tetrahedron. The iso-PrOH molecules are localized in cavities between the layers of structure II. The μeff value for complex I is 2.56 μB and indicates the absence of an appreciable interaction between the Cu2+ ions in the Cu(II)-Cl-Cu(II) exchange cluster. The compound CuLCl2· H2O (III) is synthesized. The μeff value for compound III is 1.6 μB. Complexes I and III are studied by EPR and IR spectroscopy.

The NMR technique has been applied to characterize the phototransformation products of the natural alkaloid lappaconitine. It was demonstrated that the photolysis of lappaconitine 1 results in cleavage of the ester bond with elimination of N-acetylanthranilic acid. The final reaction product was found to be an immonium salt 4 of N-acetylanthranilic acid and enamine 3. An equilibrium between the imine cation and the enamine 3 was detected.

The reaction of 1R,2R,5R-2-dimethylamino-2,6,6-trimethylbicyclo[3.1.1]heptane-3-one oxime (pinaneoxime) with Os3(CO)10(NCMe)2 was used to synthesize the (μ-H)Os3(μ-κ1-O-N=C12H21N)(CO)10 cluster with coordination of the ligand through the oxime O atom and invariable terpenoid structure. The structure of the synthesized cluster was determined by X-ray diffraction analysis. The theoretical conformational analysis of the above cluster in a solution and in crystal state was performed by a combined MM3/MERA method. The rotation of a ligand about the O(1)-N(2) bond was found impossible due to a high energy barrier (E > 550 kJ/mol).

Chiral bis-α-thiooxime (H2L1), the derivative of the natural monoterpenoid (+)-3-carene, was synthesized and used to prepare paramagnetic complexes of the composition M(H2L1)Cl2 (M=Ni, Cu). The crystal structures of [Ni(H2L1)Cl2] (I) and [Cu(H2L1)Cl2] (II) were determined by X-ray diffraction analysis. Crystals I and II consist of mononuclear acentric molecules. The Ni2+ ion in a molecule of complex I coordinates two N atoms and two S atoms of a tetradentate chelating ligand (the H2L1 molecule) and two Cl atoms. The NiCl2N2S2 coordination core forms octahedron compressed along the apical N atoms. In a molecule of complex II, the Cu2+ ion coordinates two S atoms and the N atom of a tridentate chelating H2L1 ligand and two Cl atoms. The CuCl2NS2 coordination core forms a trigonal bipyramid.

A three component condensation of 6-quinolylamine with 4-bromo-or 4-methoxybenzaldehyde, and 1,3-cyclohexanedione or dimedone gave 12-(4-bromophenyl)-and 12-(4-methoxyphenyl)-9,9-dimethyl-8,9,10,12-tetrahydro-7H-benzo[b][4,7]phenanthrolin-11-ones. The reaction intermediates obtained were N-arylmethylene-6-quinolylamines, 2-arylmethylenebis(1,3-cyclohexanediones), 3-(6-quinolylamino)-2-cyclohexenone, and 5,5-dimethyl-3-(6-quinolylamino)-2-cyclohexenone.

Coordination compounds [CoLCl2] (I), [CuLCl(NO3)] (II), CuL(NO3)2 (III), and CuLCl2 (IV) (where L is a chiral pyrazolylquinoline—a derivative of terpenoid (+)-3-carene) were synthesized. X-ray diffraction data showed that crystal structures I and II are built of mononuclear acentric molecules. In the molecule of complex I, the Co2+ ion coordinates two N atoms of bidentate cycle-forming ligand L and two Cl atoms. The coordination polyhedron of Cl2N2 is a distorted tetrahedron. For complex I, μeff = 4.50 μB, which corresponds to a high-spin configuration d 7. In the molecules of II(1), II(2) (which are diastereoisomers of complex II), each Cu2+ ion coordinates two N atoms of bidentate cycle-forming ligand L, the Cl atom, and two O atoms of bidentate cyclic NO 3 − ion. The ClN2O2 coordination polyhedra are tetragonal pyramids with different degrees of distortion. The structure of complex II consists of supramolecular clusters, i.e., isolated chains incorporating the molecules of II(1) and II(2). The values of μeff for II–IV correspond to the d 9 configuration. The results of EPR and IR study suggest that complex III contains the O4N2 polyhedron, whereas complex IV contains the Cl2N2 polyhedron. Complexes I and IV were found to show a high catalytic activity in ethylene polymerization reaction.

The copper(II) compounds [CuL](NO3)2 · H2O (I), [CuL](ClO4)2 · H2O (II), CuLCl2 · 3H2O (III), and CuLBr2 · 4H2O (IV), where L is a chiral dioxatetraazamacrocyclic ligand based on the natural monoterpene (+)-3-carene, have been synthesized. According to IR and EPR spectroscopy, L acts as a tetradentate chelating ligand coordinated through the N atoms of the NH and C=N groups. The NO 3 − anions in I and the ClO 4 − anions in II are outer-sphere. I and II have a planar coordination core CuN4, III has a CuN4ClO coordination core, and IV has a CuN4Br2 coordination core.

The synthesis of the [Cu(H2L)](NO3)2 complex (I) and of a mixed-valent complex [Cu(H2L)Cl]2[CuCl2]Cl·0.5H2O (II), where L is chiral bis(menthane) propylenediaminodioxime. According to the data of single-crystal X-ray diffraction analysis, compounds I and II have ionic structures. In complex cations, the Cu2+ ion coordinates four N atoms of tetradentate chelate ligand, namely, the H2L molecule. The coordination surrounding of the Cu atom in I is a distorted square CuN4, while in II, it is a distorted square pyramid CuN4Cl. The complex anion [CuCl2]− in II has linear structure. The mutual arrangement of oxime groups in H2L corresponds to amphi-configuration of a ligand and therefore, intramolecular hydrogen bond O...H-O are formed in H2L. The complex cations in compound II are joined in dimers through hydrogen bonds Cl...H-O. The values μeff for I and II are equal to 1.82 and 2.82 μB, respectively.

Reactions of Ni(NO3)2 · 6H2O) in EtOH(iso-PrOH) with optically active bis(menthane) ethylene-diaminodioxime (H2L1), pinano-para-menthane ethylenediaminodioxime (H2L2), pinano-para-menthane propylenediaminodioxime (H2L3) and bis(pinane) propylenediaminodioxime (H2L4) were used to synthesize [Ni(H2L1)NO3[NO3 · 2H2O (I), [Ni(HL2)]NO3 (II), [Ni(HL3)]NO3 (III), and [Ni(HL4)]NO3 (IV). X-ray diffraction study of paramagnetic complex I (μeff = 3.04 μB and diamagnetic complexes II and III revealed their ionic structures. A distorted octahedral polyhedron N4O2 in the cation of complex I is formed by the N atoms of tetradentate cycle-forming ligand, i.e., the H2L1 molecule, and the O atoms of the NO 3 − anion acting as a bidentate cyclic ligand. In the cations of complexes II and III, containing a pinane fragment, the coordination core NiN4 has the shape of a distorted square formed on coordination of tetradentate cycle-forming ligands, i.e., anions of the starting dioximes. The structure of diamagnetic complex IV is likely to be similar to the structures of complexes II and III.

Copper(II) complexes with chiral ethylenediaminodioxime (H2L1) and propylenediaminodioxime (H2L2), the derivatives of terpenoid α-pinene, of the composition [Cu(H2L1)](NO3)2 (I) and [Cu(H2L2)NO3]NO3 (II) are synthesized and studied by X-ray diffraction method. The ionic structures of I and II consist of complex cations [Cu(H2L1)]2+ (I), [Cu(H2L2)NO3]+ (II), and outer-sphere anions NO 3 − . In the cation of compound I, the Cu2+ ion (C.N.4) coordinates four N atoms of tetradentate cycle-forming ligand H2L1 with anti-configuration. The coordination surrounding of the Cu atom is a trapezoidally distorted square. In the cation of compound II, the Cu2+ ion (C.N.5) coordinates the O atom of monodentate nitro group in addition to four N atoms of tetradentate cycle-forming ligand H2L2. The coordination polyhedron of the Cu atom has the shape of a distorted square pyramid N4O. Coordinated H2L2 molecule has amphi-configuration, which is responsible for the formation of hydrogen bond between the oxime groups. The complex cations and NO 3 − anions in structures I and II are linked into ionic ensembles by hydrogen bonds.

Novel optical ligands bis(menthane) (H2L1), pinano-para-menthane (H2L2), and carano-para-menthane (H2L3) propylenediaminodioximes are obtained. Diamagentic Co(III) complexes of the composition Co(HL1)Cl2 (I), Co(HL2)Cl2 (II), Co(HL3)Cl2 (III), and Co(HL4)Cl2 · H2O(IV) are synthesized by reactions of CoCl2 with H2L1, H2L2, H2L3 and bis(carane) propylenediaminodioxime (H2L4) in ethanol in air. The crystal and molecular structures of compound I is determined by X-ray diffraction analysis. The crystals are monoclinic with the unit cell parameters a = 7.8385(3) A, b = 11.4074(6) A, c = 14.9509(6) A, β = 104.278(2)°, V = 1295.57(10) A3, Z = 2, ρ(calcd) = 1.367 g/cm3, F(000) = 564, M = 533.41, space group P21. The crystal structure of complex I consists of individual mononuclear molecules. The Co3+ ion coordinates four N atoms of tetradentate cycle-forming anionic ligand and two Cl atoms. The coordination polyhedron of Cl2N4 is a distorted octahedron. The 13C and 1H NMR spectra of the complexes synthesized confirm coordination of four N atoms of a ligand.

4-Butyl-1,2-diphenylpyrazolidine-3,5-dione derivatives were prepared by its condensation with Schiff bases formed from p-aminobenzoic acid and its methyl and ethyl esters as amine components and substituted aromatic aldehydes.

Distillation of the flowering tops of Seseli buchtormense (Fisch. ex Sprengel) W. Koch obtained from various altitudes of Altai Region yielded 0.21% (300 m.a.s.l.), 32% (400 m.a.s.l.), 30% (700 m.a.s.l.) and 0.40% (2030 m.a.s.l.), of aromatic pure mobile oil. Analysis of the oil samples using GC, GC/MS gave 82 components. The major components were sabinene (17.7–25.1%), α-pinene (5.3–14.6%), (E)-nerolidole (5.5–11.6%), β-phelandrene (2.5–7.0%), β-myrcene (3.3–6.6%), δ-kadinene (3.0–6.0%), germacrene D-4-ol (3.1–4.6%), α-bosabolol (0.0–7.7%), fenchone (0.5–7.0%) and limonene (0.8–4.5%).

Distillation of the fresh flowering tops of wild-growing Solidago virgaurea L. collected from the Russian Altai at 290 m and 650 m yielded 0.22% and 0.07% pure light yellow oil, respectively. GC and GC/MS analyses of the oils revealed that the main components from 290 m were α-pinene (36.5%), myrcene (14.8%), β-caryophyllene (10.5%), germacrene D (8.2%), β-pinene (7.1%) and limonene+β-phellandrene (6.4%). The oil from the sample collected at 650 m had benzyl benzoate (57.0%), β-caryophyllene (6.3%), germacrene D (6.0%), α-pinene (4.4%) and α-humulene (4.0%) as major components, suggesting polymorphism or the existence of different chemoytpes. Using the disc diffusion method we tested the activity of the oil obtained from 290 m against five microbes of health and environmental importance. It showed complete inhibition or killed Aspergillus niger and Staphylococcus aureus, strong inhibition of Saccharomyces cervisiae, and low activity against Escherichia coli, but no effect on Pseudomonas aeruginosa.

Mannich condensation of 3,3,5-trimethylcyclohexanone with paraformaldehyde and dimethylamine or benzylamine hydrochloride involves both activated methylene group in the initial ketone to give compounds with equatorial aminomethyl substituent. The major isomer is that formed by addition at the less sterically hindered carbon atom. Likewise, Mannich condensation of the E and Z isomers of 3,3,5-trimethylcyclohexanone oxime react at both methylene groups, and the addition of aminomethyl fragment occurs preferentially at that methylene group which is located more closely to the oxime hydroxy group.

Interaction of Co(II) chloride with optically active bis-pinane propylenediaminodioxime (H2L) gave a diamagnetic compound of Co(III) with a composition [Co(HL)Cl2]. The crystal and molecular structure of the compound was determined by X-ray diffraction (XRD) analysis (Enraf-Nonius CAD-4 diffractometer, λMoK α, 703 F hkl , R = 0.0347). The crystals are orthorhombic with unit cell parameters a = 8.989(1) A, b = 12.351(2) A, c = 22.425(3) A, V = 2487.7(6) A3, Z = 4, ρcalc = 1.420 g/cm3, space group P212121. The crystal structure of the complex is composed of discrete one-center molecules. In the complex, the Co3+ ion coordinates four N atoms of the tetradentate cycle-forming ligand (HL− anion) and two Cl atoms. The coordination polyhedron of Co is a distorted octahedron Cl2N4.