Tetrachlorozincates [Ge(LH)2][ZnCl4]∙CH3OH were isolated for the first time from isonicotinoylhydrazone 2-hydroxybenzene (2-hydroxynaphyl-1)carbaldehyde (H2L)–GeCl4–ZnCl2–CH3OH systems, in which cations are [Ge(L·H)2]2+ complexes protonated by the pyridine nitrogen atom, with L ligands tridentately coordinated via the azomethine nitrogen atom and oxygen atoms of deprotonated hydroxyazino and hydroxy groups. The complexes were studied using the methods of conductometry, thermogravimetry, IR, and 1H NMR spectroscopy.

Aim. To evaluate the influence of nicotinoylhydrazones with different molecule structure and complexes of Ge(IV) and Sn(IV) based on them on the growth of phytopathogenic fungi. Меthods. 2-hydroxy-1-naphthaldehyde nicotinoylhydrazone and 2-hydroxybenzaldehyde nicotinoylhydrazone and corresponding complexes of Ge(IV) and Sn(IV) were used in the study. Antifungal activity of studied compounds towards phytopathogenic fungi Alternaria alternata (Fr.) Keissl. F11, Botrytis cinerea Pers. F12, Pyrenophora teres Drechsler F13, Fusarium graminearum Schwabe F14, Ceratorhiza cerealis (E.P. Hoeven) R.T. Moore F15, Sclerotinia sclerotiorum (Lib.) de Bary F16 was evaluated by measurement of fungal colony diameter on the 3rd, 7th and 10th day of cultivation, and also by serial dilution method in Sabouraud broth (range of concentrations – from 25 to 100 µM). Results. Evaluation of fungal colony diameters demonstrated that studied compounds at the concentration 25 µM were able to cause significant decrease (by 17–54% compared to control) of growth of pathogen colonies. Also, mycelium development disorders were observed in Sabouraud broth at the presence of 15, 50 and 100 µM of hydrazones and metal-complexes. The most susceptible was C. cerealis F15, which growth was significantly (from 31.8 to 54.6%) inhibited by all the compounds at the concentration 25 µM, and also S. sclerotiorum (5 compounds) and A. alternata – 4 of 6 compounds. The complexes of hydrazones with tin and germanium showed more significant activity and wider antifungal spectrum compared to hydrazones they are based on. Conclusion. Studied hydrazones and based on them complexes of Ge(IV) and Sn(IV) inhibit the growth of phytopathogenic fungi which belong to both ascomycetes (Alternaria alternata, Sclerotinia sclerotiorum) and basidiomycetes (Ceratorhiza cerealis).

The [CuLBr2] complexes, where L is RRN–C(=S)–S–NHC6H11 and RR = (C2H5)2, (CH2)5, or (CH2)2O(CH2)2, have been synthesized by reacting equimolar amounts of CuBr2 in methanol and L in diethyl ether. The compounds have been studied by elemental analysis, IR spectroscopy, EPR, X-ray absorption spectroscopy, conductometry, magnetochemistry, and thermal analysis. According to IR spectroscopy data, the ligands in the complexes are bidentately coordinated to Cu(II) through the thione sulfur sulfenamide and nitrogen atoms. Exact structural parameters of the nearest environment of Cu(II) have been determined from analysis of Cu and Br K-edge EXAFS spectra. The Cu–N, Cu–S, and Cu–Br bond lengths are within 2.06–2.08, 2.24–2.49, and 2.33–2.38 Å, respectively. The EPR spectra of the complexes in a DMF solution at 293 K are described by the isotropic spin Hamiltonian with spin S = 1/2, including hyperfine coupling to the nuclear spin of the central copper atom and additional hyperfine coupling to the nuclear spins of two equivalent bromine atoms and one nitrogen atom.

By interaction of SnCl4 with condensation products of dihydrazides of oxalic, terephthalic, malonic acids and R-benzoic aldehydes (R = Н, 4-N(CH3)2, 2-OH) in acetonitrile, the following complexes were synthesized: with oxaloyl- [SnCl4(H2Oxb)]∙CH3CN (R = Н, I), [SnCl4(Oxdb∙2H)]·2CH3CN (R = 4-N(CH3)2, II), [SnCl4(H4Oxs)]∙CH3CN (R = 2-OH, III), терефталоїл- [(SnCl4)2(μ-Tfdb·2H)]∙2CH3CN (R = 4-N(CH3)2, IV), [SnCl4(μ-H2Tfs)]∙CH3CN (R = 2-OH, V), malonoyldihydrazones- [SnCl4(μ-Maldb·2H)]·2CH3CN (R = 4-N(CH3)2, VI), [SnCl4(μ-H2Mals)] ∙ CH3CN (R = 2-OH, VII). Their composition and structure are established by the methods of elemental analysis, conductometry, thermogravimetry, and IR spectroscopy. It was established that in the absence of a spacer (X = 0) in the dihydrazone molecules of R-benzoic aldehydes (R = H, 2-OH, 4-N(CH3)2) – oxaloyl dihydrazones, regardless of the presence of functional groups (CН=N, OH) as part of these molecules, SnCl4 forms only mononuclear complexes I-III with the same O,O- coordination and composition of the coordination node, the charge of which is determined by a substituent (R) in the aldehyde fragment: R = H, 2-OH – {SnCl4O2}, R = 4-N(CH3)2 – {SnCl4O2}2-. In the presence of a spacer in dihydrazone molecules, regardless of their stereochemical rigidity (X = -C6H4-, -CH2-), only if R = 2-OH, 4-N(CH3)2, binuclear Sn(IV) complexes are formed with spatially separated coordination nodes, the composition of the nodes and the dihydrazone denatism is been determined by the substituent (R): R = 4-N(CH3)2 – {SnCl4ON}2- (tetra- in IV, VI), R = 2-OH – {SnCl3O2N} (hexacoordinated ligand in V, VII). Coordination of dihydrazones in a enol form, both in mono- (II) and in binuclear complexes (IV, VI), is a consequence of the presence of vacant nitrogen atoms in the aldehyde fragments of their molecules (R = 4-N(CH3)2); due to their protonation, a negative charge is compensated, which is localized in this case at the coordination sites of the zwitterionic complexes {SnCl4O2}2- (II) and {SnCl4ON}2- (IV, VI). The patterns of the formation of each spatially separated coordination node and the tautomeric form of the ligands in IV-VII are the same as in mononuclear tin(IV) complexes.

Сomplexes[SnCl4(R-Ib∙Н)], where R=H (1), 4-Br (2), 4-NO2(3), 2-OCH3(4), 4-OCH3(5), -ОC7H15(6),were synthesized by interaction of SnCl4 with isonicotinoylhydrazones of R-benzoic aldehydes (R-HIb) in acetonitrile and complex [SnCl3(2-OH-Inf∙Н)](9) – by interaction of SnCl4with 2-OH- naphthaldehydeisonicotinoylhydrazone (2-OH-H2Inf). In (1-6) bidentateO(C-O)–N(N=CH)-coordination of the enol form of the ligand is realized and the coordination node {SnCl4ON}– is formed, and in (9) the enol form remains, but the composition of the node changes – {SnCl3O2N}– due to O(C-O)–N(N=CH)–О(Ph-O)- tridentate coordination.The compounds were characterized by the methods of elemental analysis, mass spectrometry, conductometry, thermogravimetry. Their structure was established by comparing the mass- and IR spectra (1-6) and (9) with previously obtained and X-ray structurally characterized complexes [SnCl4(R-Ib∙Н)]∙CH3CN (R=4-N(CH3)2(7)) and [SnCl3(R-Ib∙Н)]∙2CH3CN (R=2-OH(8))with bi- (7) and tridentate coordination (8) of isonicotinoylhydrazones, respectively. It is shown that (1-6) and (9) are complex compounds of the zwitterionic type: the negative charge on the coordination nodes of tin(IV)is delocalized by the oxyazine fragment N=C–O, and the positive charge – by the protonation of the vacant pyridine nitrogen atomof hydrazide fragment. The influence of the composition of the coordination node of complexes (1-9), as well as the nature and position of the substituents (R) in their molecules on the activity against Mycobacteriumtuberculosis was determined. It was found that the effect of complexes with tridentate hydrazones (8) and (9) on the growth of pathogen is lower (MIC = 12.5 and 25 μM/ml, respectively) compared with bidentatehydrazones (MIC (1-7) = 0,8 – 6,25 μM/ml), among which [SnCl4(2-OCH3-Ib∙Н)] (4) stand out (MIC = 0.8 μM/ml).

The interaction in the GeCl 4 –nicotinoyl(isonicotinoyl, 2-, or 4-aminobenzoyl) hydrazone of 2-hydroxybenz(2-hydroxy-1-naphth)aldehyde (H 2 L)–CoCl 2 –methanol systems has resulted in the formation of [Ge(L·H) 2 ][CoCl 4 ]· n CH 3 OH complexes with germanium chelates [Ge(L·H) 2 ] 2+ protonated at the exo chelate nitrogen atom (N Py or NH 2 ) as the cation. The type of electrolytic dissociation and character of thermolysis of the complexes have been revealed. Spectral, thermal, and magnetic properties of the complexes have been studied.

The lipopolysaccharides (LPS) of the seven strains of Pantoea agglomerans were isolated and chemically identified. It was established that the investigated strains characterized by different relative output of LPS from 5.2 to 14.0 % by dry weight of bacteria. LPS were characterized quite high content of carbohydrates - from 22 to 54 % 2-keto-3-deoxyoctonic acid (KDO) - from 0.39 to 2.22 % and heptose - from 3.3 to 14.00 %. Fatty acids, containing in the chain of 12 to 16 carbon atoms were identified. Lipids A of all tested LPS were characterized by predominant 3-OH-C14:0 acid from 31.7 to 39.3 % depending on the strain. Since all the studied strains of P. agglomerans were sensitive to polymyxin B, it can be concluded that the LPS do not contain in the structure of lipid A, such a substitute as 4-amino-4-deoxy-L-arabinose. One of the ways of changes in the functional and biological properties of LPS is the chemical modification. As modifiers were used complexes of germanium and tin. In the study of serological activity and toxicity of modified LPS it was found that some of them lost both serological and toxic activity. It was revealed that all investigated P. agglomerans LPS decreased the median adhesion and the index of the adhesiveness. The higher concentration of P. agglomerans LPS in the reaction mixture, the less interactions between surface structures of red blood cells and E. coli cells.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

The complexes of composition [SnCl3L]nCH3CN (n=0—2) have been obtained by SnCl4 interaction with 2-hydroxy(benz)-1-naphthaldehydes benzoyl-(salicyloyl)hydrazones in acetonitrile. It was proved by methods of electronic, IR- and PMR spectroscopy ligands molecules to be coordinated by tin atom as tridentate ones via azomethine group nitrogen atom and carbonyl and oxy-groups oxygen atoms. The thermal stability of obtained compounds has been studied. The structure schemes are offered.

Complexes of different types: molecular chelates [SnCl4(HL1,2)]∙nCH3CN (I, II) and zwitterionic [SnCl4(L∙H3-6)] ∙ nCH3CN (III-VI) – were synthesized by interaction of SnCl4 withsalicyloyl-(HL1,2), β-,γ- pyridinoyl)hydrazones (НL3-6) of 2- and 4-methoxyaldehydes. Complexes I, II, unlike III-VI, are subjected to solvolysis in DMF by the reaction: [SnCl4(HL1,2)]∙+ДМФА → [SnCl3(HL1,2)(ДМФА)]∙+ Cl–. The mass spectra of I, II contains peaks of ions with m/z 36[HCl]+, 225[SnCl3]+ and hydrazone 270[HL1,2]+, spectra of III-VI – 36[HCl]+ and480[120SnCl3(L3-6)]+. In the IR spectra of I, II bands ν(C=O), ν(NH) are displaced to lower frequencies as compared to hydrazones; in the spectra of III-VI they are absent; in I–VI appear new ν(Sn–О) and ν(Sn–N), retained frequency νas(СН3)/νs(СН3), νas(CAr-O-C) and ν(ОH) (I, II). This indicated, that in I–VI realized bidentate coordination of hydrazones in different forms: ketone О(С=О)–N(CH=N) (I, II) or enol О(С–О)–N(CH=N) (III–VI) in the presence of a protonated (HN+Ру) pyridine nitrogen atom. Thermolysis of I–VI begins by dehydrochlorination, which for III–VI occurs at a higher temperature:~ 230(III, V) and 275 (IV, VI) with formationof the final product SnO2. A primary screening of hydrazones and II, V, VI on the manifestation of antimicrobial activity was conducted, it is shown that depending on the concentrationsof 25, 50 and 100 mcg/ml they able to significantly inhibit or induce the accumulation of biomass strains of E. coli, S. аureus, B. subtilis. It was found 100% inhibition complex II of all cultures and VI – only B. subtilis.

Rhodium-catalyzed hydroformylation of dicyclopentadiene using different kinds of mono- and bidentate phosphorus ligands was studied. The results demonstrated that the electronic and steric properties of ligand could influence the catalytic activity and the selectivity towards dialdehyde products. High conversion (99.9%) and good selectivity (95.0%) to dialdehydes were achieved under optimized reaction conditions in the presence of Rh/mixed mono- and bidentate phosphorus ligand complex (bidentate ligand: 2,2′-bis(dipyrrolylphosphinooxy)-1,1′-(±)-biphenyl (L1) and monodentate ligand: tri-(4-methoxylphenyl)phosphine (L8) (L1/L8 molar ratio 1/2)), which offers an easy approach to prepare dialdehydes from hydroformylation of cyclopentadiene under mild conditions (5.0 MPa, 100 °C).

Вісник Одеського нац. університету: сер.: Хімія : науковий журнал / ОНУ ім. І.І. Мечникова . – Одеса : ОНУ ім. І.І. Мечникова, 2016

The information on types of coordination of benzoyl-(2-hydroxybenzoyl-, pyridinoyl-)hy- drazones of benz-(2-hydroxybenz)aldehydes in d-metal complexes is given in the review. The results of systematic investigations of interaction between hydrazones of substituted benz-(-1- naphth)aldehydes and Lewis acids (GeCl4, SnCl4) in methanol (acetonitrile)carried by authors, are generalized. About 45 germanium and tin compounds have been synthesized for the first time (15 of them - X-ray analysis). The influence of structure of hydrazide (R-benzoyl-(R = H, OH, NO2, Cl, NH2), alpha-, beta-, gamma-pyridinoyl-) and aldehyde (benz-, 4-dimethylaminobenz-, 2-hydroxybenz-, 2-hydroxy-1-naphth-) trayments of hydrazone molecule, central ion(Ge(IV), Sn(IV)), solvent nature (CH3OH, CH3CN) on composition, structure of complexes and ligands coordination form have been proved. The prospect of complexes use as anti-inflammatory and antimicrobial drugs have been shown.

The influence of izonicotinoilhydrazone 2-hydroxynapht-(H2Inf, I), 4-dimethilamin-obenzaldehydes (HIdb(II)) and its complexes with tin(IV) [SnCl3(InfH)] (III), [H2InfH]2[SnCl6] (IV), [SnCl3(IdbH)] (V) on the opportunistic bacteria growth has been investigated. It has been shown that studied compounds are able to suppress the biomass increase of S. aureus, P. aeruginosa, B. subtilis, M. luteusand P. vulgaris test-strains at concentrations 25, 50 and 100 pg per ml. All compounds have demonstrated the highest activity towards P. vulgaris. The most wide spectrum of antimicrobial activity have demonstrated compounds I, IV.

By the method of self-assembly of the reacting components in the systems “GeCl4 — pyridinoylhydrazones 2-hydroxybenz- (a-, p-, y-H2Ls) and 2-hydroxy- 1-naphth-aldehydes (H2Lnf) — CoCl2 - methanol” six complexes of the composition [Co(Cl)(H2O)(|i-Ls)2Ge]Cl 2H2O (I-III) and [Co(Cl)(H2O)(p-Lnf)2Ge]C12H2O (IV-VI) have been synthesized. Their electrolytic dissociation type and thermolysis character have been stated. It has been stated by the methods of IR spectroscopy, diffuse reflectance spectra, and magnetic susceptibility measurements two ligands in the (I-VI) to be bridged, doubly deprotonated (Ls2_, Lnf2 ), and tridentately linked to germanium (O(C-O) - N(ch=n) – O (Ph-O)) and monodentately linked to cobalt ion via pyridine nitrogen atom. At that germanium geometry holds the octahedral (Ge04N2) and cobalt one forms the tetrahedral shape.

The reaction of SnCl4 with 2-hydroxybenz(2-hydroxynaphth)aldehyde nicotinoylhydrazones (H2Ns, H2Nnf) in CH3OH gave non-electrolyte complexes [SnCl3(HNs)] (I) and [SnCl3(HNnf)] (II), which were recrystallized to give the solvates [SnCl3(HNs)] · DMF (III) and [SnCl3(HNnf)] · 2DMF (IV). It was found by IR spectroscopy that the ligands in I–IV are protonated at the N(Py) and coordinated in the tridentate chelating mode through the azomethine nitrogen atom and oxy and oxyazine oxygen atoms. The thermolysis of I–IV and electron impact-induced fragmentation of I and II are accompanied by the formation of the complexes [SnCl2(Ns)] and [SnCl2(Nnf)]. The molecular and crystal structures of IV were determined by X-ray diffraction (CIF file CCDC no. 816105).

The principle possibility of obtaining condensation products R-benzoic aldehyde (R = H, 4-N(CH3)2, 2-OH) and zwitterionic complexes of SnCl4with hydrazides 2- and 4- aminoben-zoic acids. It is proved (IR, mass spectrometry, thermal gravimetric analysis, conductivity), that in the complexes that are formed, аlso implemented enol form of the ligand (hydra- аlso implemented enol form of the ligand (hydra- lso implemented enol form of the ligand (hydra-zone). In the case of bidentate coordination (R = H, 4-N(CH3)2) remains the coordinating node {SnCl4ON}-, which is characteristic for hydrazide complexes and when tridentate (R = 2-OH) – it varies {SnCl3O2N}-.