Synthesis and characterization of the [Ru<Subscript>3</Subscript>O(CH<Subscript>3</Subscript>COO)<Subscript>6</Subscript>(py)<Subscript>2</Subscript>(BPE)Ru(bpy)<Subscript>2</Subscript>Cl](PF<Subscript>6</Subscript>)<Subscript>2</Subscript> dimer

The polymetallic [Ru₃O(CH₃COO)₆(py)₂(BPE)Ru(bpy)₂Cl](PF₆)₂ complex (bpy = 2,2′-bipyridine, BPE = trans-1,2-bis(4-pyridil)ethylene and py = pyridine) was assembled by the combination of an electroactive [Ru₃O] moiety with a [Ru(bpy)₂(BPE)Cl] photoactive centre, and its structure was determined using positive ion electrospray (ESI-MS) and tandem mass (ESI-MS/MS) spectrometry. The [Ru₃O(CH₃COO)₆(py)₂(BPE)Ru(bpy)₂Cl]²⁺ doubly charged ion of m/z 732 was mass-selected and subject to 15 eV collision-induced dissociation, leading to a specific dissociation pattern, diagnostic of the complex structure. The electronic spectra display broad bands at 409, 491 and 692 nm ascribed to the [Ru(bpy)₂(BPE)] charge-transfer bands and to the [Ru₃O] internal cluster transitions. The cyclic voltammetry shows five reversible waves at −1.07 V, 0.13 V, 1.17 V, 2.91 V and −1.29 V (vs SHE) assigned to the [Ru₃O]^{−1/0/+1/+2/+3} and to the bpy^0/−1 redox processes; also a wave is observed at 0.96 V, assigned to the Ru^+2/+3 pair. Despite the conjugated BPE bridge, the electrochemical and spectroelectrochemical results indicate only a weak coupling through the π-system, and preliminary photophysical essays showed the compound decomposes under visible light irradiation.     

Studies on the copolymerization of norbornene with CO catalyzed by a new catalytic system PdCl<Subscript>2</Subscript>/phen/M(CF<Subscript>3</Subscript>SO<Subscript>3</Subscript>)<Subscript>n</Subscript>

A new three-component catalytic system, PdCl₂/phen/M(CF₃SO₃)_n where M = La, Y, Yb, Zn, and Cu, was studied for the copolymerization of norbornene (NBE) with CO to prepare polyketone (PK). It was found that the CF₃SO₃H catalytic system gave a low catalytic activity for the copolymerization of norbornene with CO, but when M(CF₃SO₃)_n was introduced instead of CF₃SO₃H, the PdCl₂/phen/M(CF₃SO₃)_n catalytic system exhibited much higher activity. The effects of ligands, M(CF₃SO₃)_n, solvents, and temperatures on the copolymerization have been discussed in detail. The results showed that with 1,10-phenanthroline (phen) and Cu(CF₃SO₃)₂ used as cocatalysts, the corresponding reaction rate reached 82 000 g PK (mol Pd)⁻¹h⁻¹ when the reaction was carried out in methanol at 90°C and 3.0 MPa of CO, and the weight average molecular weight (M _w) of the resultant copolymer is 1090 g/mol. The copolymer was characterized with various techniques such as FT-IR, ¹HNMR, ¹³CNMR, TGA, and DSC. The infrared spectrum of the product includes two features at 1697 and 1732 cm⁻¹ for the NBE/CO copolymer in CH₃OH that are attributed to carbonyl groups in ketones (repeating unit) and esters (end group), respectively. Due to the tension of the ring of norbornene, the degree of copolymerization is not high. Published in Russian in Kinetika i Kataliz, 2007, Vol. 48, No. 1, pp. 51–58. This article was submitted by the authors in English.     

Reaction of the novel Ru<Subscript>3</Subscript>(CO)<Subscript>10</Subscript>[Ph<Subscript>2</Subscript>P(CH<Subscript>2</Subscript>)<Subscript>2</Subscript>Si(OEt<Subscript>3</Subscript>)]<Subscript>2</Subscript> complex on SBA-15 and MCM-41 mesoporous silicas

The reaction of Ru₃(CO)₁₂ with 2(diphenylphosphino)ethyl-triethoxysilane (DPTS) in hydrocarbons, leads to the functionalized Ru₃(CO)_12−n [Ph₂P(CH₂)₂Si(OEt₃)] _n (n = 1,2) complexes. The complex with two phosphine substituents was chemically anchored on mesoporous silicas, SBA-15 and MCM-41, in order to obtain two hybrid materials characterized by a different localization of the metal centre on the surface of the porous supports. A detailed investigation of the cluster, before and after chemical anchoring on the mesoporous silicas, was pursued. Particular attention was also devoted to the study of the morphological, structural and textural properties of the metal-functionalised silicas (Ru/SBA-15 and Ru/MCM-41) by infrared spectroscopy (FT-IR), scanning electron microscopy, X-ray diffraction and N₂ physisorption analysis.     

Investigation into the formation of heteronuclear clusters of formula [{Ru<Subscript>6</Subscript>C(CO)<Subscript>16</Subscript>Ag<Subscript>2</Subscript>X}<Subscript>2</Subscript>]<Superscript>2−</Superscript> (X = Cl,Br or I)

Reaction of [Ru₆C(CO)₁₆]²⁻ with an excess of AgX (X = Cl, Br or I) affords heteronuclear clusters of formula [{Ru₆C(CO)₁₆Ag₂X}₂]²⁻ in 80% yield, which for X = I and X = Br/Cl were crystallographically characterised. The formation of the cluster was followed in solution using electrospray ionisation mass spectrometry (ESI-MS), which revealed the presence of a wide range of clusters with the general formula [{Ru₆C(CO)₁₆} _x Ag _y X _z ]^{(2x−y+z)−} where x = 1 or 2, y = 1, 2, 3 or 4 and z = 0, 1 or 2. The high yield of the product despite the evident complicated solution speciation is attributed to selective crystallisation of the observed compound driving the equilibrium toward this product.     

Multifunctional iron thiocarboxylate complexes: synthesis,reactivity and structure of CpFe(CO)<Subscript>2</Subscript>SCO-3,5-C<Subscript>6</Subscript>H<Subscript>4</Subscript>(COCl)<Subscript>2</Subscript>

A controlled substitution reaction of the chlorine atoms of 1,3,5-benzenetricarbonyl trichloride by the organoiron fragment (CpFe(CO)₂S) has been achieved. The complexes CpFe(CO)₂SCO-3,5-C₆H₃(COCl)₂ (1), 1,3-[CpFe(CO)₂SCO]₂-5-C₆H₃COCl (2) and 1,3,5-[CpFe(CO)₂SCO]₃C₆H₃ (3) were prepared from the reaction of (μ-S _x )[CpFe(CO)₂]₂ (x = 3, 4) with 1,3,5-C₆H₃(COCl)₃ in a 1:1, 2:1, or 3:1 metal to ligand molar ratio. The reactions of (1) with amines, thiols, and carboxylic acids produce the trifunctional mono-iron complexes CpFe(CO)₂SCO-3,5-C₆H₃(COY)₂ [Y = NR₂ (4), SR (5), OCOR (4)]. The X-ray structure determination of (1) is reported.     

Synthesis and crystal structure of a mixed valence heteropoly green compound, (PPh<Subscript>4</Subscript>)<Subscript>4</Subscript>[PMo<Subscript>12</Subscript>O<Subscript>40</Subscript>], and its use as a catalyst in olefin epoxidation

A green heteropolyblue compound, (PPh₄)₄[PMo₁₂O₄₀] · 3DMF(1), has been synthesized from MoO₃, H₂O₂ and H₃PO₄ in acetylacetone medium and crystallized from N,N-dimethylformamide. Compound 1 was characterized by analytical and spectroscopic methods, and X-ray structure analysis. The compound is a one-electron paramagnet and shows a featureless and cubic EPR spectrum with <g> = 1.95 in DMF glass. The complex shows a Mo(V)–Mo(IV) couple, which has been studied by cyclic voltammetric and coulometric methods. The compound acts as an efficient olefin epoxidation catalyst with H₂O₂ as oxidant and NaHCO₃ as co-catalyst. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Ruthenium Carbonyl Cluster Complexes with Phenylgermyl Ligands from the Reactions of Ph<Subscript>3</Subscript>GeH with Ru(CO)<Subscript>5</Subscript> and Ru<Subscript>3</Subscript>(CO)<Subscript>12</Subscript>

Four new triphenylgermylruthenium carbonyl compounds HRu(CO)₄GePh₃, 14; Ru(CO)₄(GePh₃)₂, 15; Ru₂(CO)₈(GePh₃)₂, 16; and Ru₃(CO)₉(GePh₃)₃(μ-H)₃, 17 were obtained from the reaction of Ru(CO)₅ with Ph₃GeH in hexane solvent at reflux, 68 °C. The major product 14 was formed by loss of CO from the Ru(CO)₅ and an oxidative addition of the GeH bond of the Ph₃GeH to the metal atom. This six coordinate complex contains one terminal hydrido ligand. Compound 15 is formed from 14 and contains two trans-positioned GePh₃ ligands in the six coordinate complex. Compound 16 contains two Ru(CO)₄(GePh₃) fragments joined by an Ru–Ru single bond. Compound 17 contains a triangular cluster of three ruthenium atoms with three bridging hydrido ligands and one terminal GePh₃ ligand on each metal atom. When heated to 125 °C, 14 was converted to the new triruthenium compound Ru₃(CO)₁₀(μ-GePh₂)₂, 18. Compound 18 consists of a triangular tri-ruthenium cluster with two GePh₂ ligands bridging two different edges of the cluster and one bridging CO ligand. Ru₃(CO)₁₂ was found to react with Ph₃GeH at 97 °C to yield three products: 15, and two new compounds Ru₃(CO)₉(μ-GePh₂)₃, 19 and Ru₂(CO)₆(μ-GePh₂)₂(GePh₃)₂, 20 were obtained. Compound 19 is similar to 18 having a triangular tri-ruthenium cluster but has three bridging GePh₂ ligands, one on each Ru–Ru bond. Compound 20 contains only two ruthenium atoms joined by a single Ru–Ru bond that has two bridging GePh₂ ligands and a terminal GePh₃ ligand on each metal atom. All compounds were characterized by a combination of IR, ¹H NMR, single-crystal X-ray diffraction analyses. This report is dedicated to Professor Dieter Fenske on the occasion of his 65th birthday for his many pioneering contributions to the chemistry of metal chalcogenide cluster complexes.     

Pyridyl derivatives provide new pathways for labeling protein with fac-[<Superscript>188</Superscript>Re(CO)<Subscript>3</Subscript>(H<Subscript>2</Subscript>O)<Subscript>3</Subscript>]<Superscript>+</Superscript>

The purpose of this work was to indirect label IgG with fac-[¹⁸⁸Re(CO)₃(H₂O)₃]⁺ and to check the radiochemical behavior of the labeled product. The compound of (bis(2-pyridylmethyl)-amino)-acetic acid (L²H) was synthesized and labeled with fac-[¹⁸⁸Re(CO)₃(H₂O)₃]⁺. The labeling yield of ¹⁸⁸Re(CO)₃–L²H was more than 90%. The effects of protein concentration, reaction time, pH and reaction temperature of labeling of IgG with ¹⁸⁸Re(CO)₃–L²H were investigated. The conjugation conditions were optimized. The labeled product was analyzed by size exclusion HPLC and TLC. The stability of ¹⁸⁸Re(CO)₃–L²H–IgG in vitro was high. The results of this study may be useful for [¹⁸⁸Re(CO)₃(H₂O)₃]⁺ labeling of protein for radioimmunotherapy.     

Synthesis,characterization, and biphasic ionic liquid media 1-hexene hydrogenation reaction of RuCl<Subscript>2</Subscript>(DMSO)<Subscript>2</Subscript>(NC<Subscript>5</Subscript>H<Subscript>4</Subscript>CO<Subscript>2</Subscript>Na-3)<Subscript>2</Subscript>

RuCl₂(DMSO)₂(NC₅H₄CO₂Na-3)₂ is very soluble in the ionic liquid (IL) 1-n-butyl-3-methylimidazolium tetrafluoroborate, [(BMIM)BF₄]. The complex was prepared by reacting RuCl₂(DMSO)₄ with NC₅H₄CO₂Na-3, sodium nicotinate, in toluene, and was characterized by spectroscopic methods. The complex catalyzes the hydrogenation of 1-hexene (600 psi H₂, 100 °C) in a two-phase system consisting of cyclohexane/[(BMIM)BF₄] with 75% conversion in 24 h and modest substrate isomerization. The complex shows good stability and can be reused several times with little loss in activity.     

Synthesis,crystal structure,and thermal decomposition kinetics of complex [Nd(BA)<Subscript>3</Subscript>bipy]<Subscript>2</Subscript>

The complex of [Nd(BA)₃bipy]₂ (BA = benzoic acid; bipy = 2,2′-bipyridine) has been synthesized and characterized by elemental analysis, IR spectra, single crystal X-ray diffraction, and TG/DTG techniques. The crystal is monoclinic with space group P2(1)/n. The two–eight coordinated Nd³⁺ ions are linked together by four bridged BA ligands and each Nd³⁺ ion is further bonded to one chelated bidentate BA ligand and one 2,2′-bipyridine molecule. The thermal decomposition process of the title complex was discussed by TG/DTG and IR techniques. The non-isothermal kinetics was investigated by using double equal-double step method. The kinetic equation for the first stage can be expressed as dα/dt = A exp(−E/RT)(1 − α). The thermodynamic parameters (ΔH ^≠, ΔG ^≠, and ΔS ^≠) and kinetic parameters (activation energy E and pre-exponential factor A) were also calculated.     

Interpretation of the difference of optimal Mo density in MoS<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and MoS<Subscript>2</Subscript>-TiO<Subscript>2</Subscript> HDS catalysts

The first part of this paper deals with the morphology of the MoS₂ phase and its oxide precursor, the MoO₃ phase, mainly from a geometrical point of view. After giving a brief review of the literature describing the structure of these compounds, Mo densities in both phases were calculated along various crystallographic planes. Further, using structural models recently proposed by others, Mo densities in MoS₂ were also calculated in the case of an epitactic growth on γ-Al₂O₃ and TiO₂ model surfaces. Then, the calculated Mo densities were compared with experimental results (Mo density when HDS activity is maximal) previously obtained for catalysts constituted of MoS₂ supported on a low SSA TiO₂, a high SSA TiO₂ and a conventional γ-alumina. It was suggested that either on alumina or titania the MoS₂ phase is growing as (100) MoS₂ planes. However, while on the alumina the optimal MoS₂ phase might be constituted of dispersed MoS₂ slabs covering only a part of the alumina surface (2.9–3.9 Mo atoms/nm²), on titania the optimal MoS₂ phase might be constituted of a uniform MoS₂ monolayer (5.2 atoms/nm² for the high SSA titania, which is equal to the Mo density of a perfect MoS₂ (100) plane). This difference may originate in the creation of a 'TiMoS' phase enhancing the S atoms mobility over Mo/TiO₂-sulfided catalysts. Indeed, while in the case of a γ-alumina carrier the active sites (labile S atoms) are located on the edge of MoS₂ slabs making the ratio Mo_edge/Mo_total a crucial parameter for the catalytic performances, in the case of a titania carrier the labile sulfur atoms might be statistically distributed all over the TiMoS active phase. Further, the higher Mo density observed over the high SSA titania (5.2 atoms/nm²) when compared to that over the low SSA titania (4.2 atoms/nm²) was supposedly due to the pH-swing method advantageously used to prepare the former carrier. Indeed, this method allows giving a solid with enhanced mechanical properties providing a good stability to the derived catalysts under experimental conditions. In addition, this TiO₂ carrier exhibits a great homogeneity, with a surface structure substantially uniform, which might be adequate for a long-range growth of (100) MoS₂ slabs.     

Synthesis and characterization of η<Superscript>3</Superscript>-allyl palladium(II) complexes with Ph<Subscript>2</Subscript>P(S)CHP(S)Ph<Subscript>2</Subscript> and OC(CF<Subscript>3</Subscript>)CHCO(C<Subscript>4</Subscript>H<Subscript>3</Subscript>S) co-ligands

The new complexes [(η³-Me₂CCMeCH₂)Pd{η²-Ph₂P(S)CHP(S)Ph₂] (1), [(η³-Me₂CCMeCH₂)Pd{η²-OC(CF₃) CHCO(C₄H₃S)}] (2) and [(η³-CH₂CMeCH₂)Pd{η²-OC(CF₃)CHCO(C₄H₃S)}] (3) have been synthesized by reacting [(η³-allyl)Pd(μ-Cl)]₂ with Ph₂P(S)CH₂P(S)Ph₂ and OC(CF₃)CH₂CO(C₄H₃S) in the presence of base. All have been characterized by elemental analysis, FT-IR, ¹H-n.m.r and FAB-mass spectroscopy. Spectroscopic studies suggest that both ligands are bidentate, forming six-membered Pd-S-P-C-P-S and Pd-O-C-C-C-O palladacycles, the η³-allyl group completing the coordination sphere.     

Synthesis of pyridyl derivatives for the future functionalization of biomolecules labeled with the fac-[<Superscript>188</Superscript>Re(CO)<Subscript>3</Subscript>(H<Subscript>2</Subscript>O)<Subscript>3</Subscript>]<Superscript>+</Superscript> precursor

In this paper, we investigated three ligand systems, symmetric and asymmetric pyridyl-containing tridentate ligands (L¹NH₂ = (bis(2-pyridylmethyl)-amino)-ethylamine, L²H = (bis(2-pyridylmethyl)-amino)-acetic acid, L³NH₂ = [(6-amino-hexyl)-pyridyl-2-methyl-amino]-acetic acid) as bifunctional chelating agents for labeling biomolecules. These ligands reacted with the precursor fac-[¹⁸⁸Re(CO)₃(H₂O)₃]⁺ and yielded the radioactive complexes fac-[¹⁸⁸Re(CO)₃L] (L = three ligands), which were identified by RP-HPLC. The corresponding stable rhenium tricarbonyl complexes (1–3) were allowed for macroscopic identification of the radiochemical compounds. ¹⁸⁸Re tricarbonyl complexes, with log P _o/w values ranging from −1.36 to −0.32, were obtained with yields of ≥90% using ligand concentrations within the 10⁻⁶−10⁻⁴M range. Challenge studies with cysteine and histidine revealed the high stability properties of these radioactive complexes, and biodistribution studies in normal mice indicated a fast rate of blood clearance and high rate of total radioactivity excretion, primarily through the renal-urinary pathway. In summary, these asymmetric and symmetric pyridyl-containing tridentate ligands are potent bifunctional chelators for the future biomolecules labeling of fac-[¹⁸⁸Re(CO)₃(H₂O)₃]⁺.     

Synthesis and characterization of macroporous Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>/C composites as cathode materials for Li-ion batteries

The macroporous Li₃V₂(PO₄)₃/C composite was synthesized by oxalic acid-assisted carbon thermal reaction, and the common Li₃V₂(PO₄)₃/C composite was also prepared for comparison. These samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), and electrochemical performance tests. Based on XRD and SEM results, the sample has monoclinic structure and macroporous morphology when oxalic acid is introduced. Electrochemical tests show that the macroporous Li₃V₂(PO₄)₃/C sample has a high initial discharge capacity (130 mAh g⁻¹ at 0.1 C) and a reversible discharge capacity of 124.9 mAh g⁻¹ over 20 cycles. Moreover, the discharge capacity of the sample is still 91.5 mAh g⁻¹, even at a high rate of 2 C, which is better than that of the sample with common morphology. The improvement in electrochemical performance should be attributed to its improved lithium ion diffusion coefficient for the macroporous morphology, which was verfied by cyclic voltammetry and electrochemical impedance spectroscopy.     

XAFS investigation of [Pd(NH<Subscript>3</Subscript>)<Subscript>4</Subscript>][AuCl<Subscript>4</Subscript>]<Subscript>2</Subscript> and its thermolysis products

Thermolysis of double complex salt [Pd(NH₃)₄][AuCl₄]₂ has been studied in helium atmosphere from ambient to 350 °C. The XAFS of Pd K and Au L₃ edges and thermogravimetry measurements have been carried out to characterize the intermediates and the final product. In the temperature range 115–160 °C the complex is decomposed to form Pd(NH₃)₂Cl₂ and AuCl_4−x N _x species with x ranging from 2 to 3. Subsequent heating of the intermediate up to 300 °C leads to the total loss of NH₃. The Au–Cl and Au–Au bonds form the local environment of Au at the stage of decomposition while only four chlorine atoms are around Pd. At the temperature of 330 °C the Au and Pd nanoparticles as well as residues of palladium chloride are detected. The final product consists of separated Au and Pd nanoparticles.     

Synthesis,characterization and thermal stability of complex <Emphasis Type="Italic">cis</Emphasis>-[Co(bipy)<Subscript>2</Subscript>(CN)<Subscript>2</Subscript>] and its interaction with NO<Subscript>2</Subscript> gas

cis-[Co(bipy)₂(CN)₂] complex was successfully prepared from the reaction of [Co(CN)₂] with 2,2′-bipyridine in ethanol 96%. The product of complex synthesized was light brown crystal with percent yield of 75.86%. The IR spectrum of this complex showed strong characteristics vibration band at 1471.9 and 1442.75 cm⁻¹ for C=N stretching, 1664.57 cm⁻¹ for C=C aromatic, 1600.9 cm⁻¹ 1 for HC=CH aromatic, 653.87 cm⁻¹ for pyridine ring on 2,2′-bipyridine ligand, 3109.25 and 3080.32 cm⁻¹ for C-H of aromatic ring. The thermogram of DTA-TG analysis showed 4 endothermic peaks at temperature of 53.4, 323.2, 444.2, and 526.4°C, where the bond breaking of the complex occurred at different temperatures. The result of moment magnet measurement of the complex showed that it was a high spin complex with moment magnet value of 3.68 BM, so it is a paramagnetic complex.     

One-pot synthesis of diphenyl pyrazolylmethylanilines via reductive amination using NaBH<Subscript>4</Subscript>/I<Subscript>2</Subscript> and their antimicrobial screening

Abstract  

Direct reductive amination of 1,3-diphenyl-1H-pyrazole-4-carbaldehyde and 3-(4-methylphenyl)-1-phenyl-1H-pyrazole-4-carbaldehyde with various substituted aromatic amines using NaBH₄ in the presence of I₂ as reducing agent is described. The reaction has been carried out in anhydrous methanol under neutral conditions at room temperature. The structure of newly synthesized diphenyl pyrazolylmethylanilines was established on the basis of IR, ¹H, ¹³C NMR, and mass spectral data. All diphenyl pyrazolylmethylaniline derivatives were tested in vitro for their antifungal and antibacterial activity against different strains of fungi and bacteria. Most of the compound exhibited considerable antifungal activity but poor antibacterial activity against the test strains.     

Kinetics of the uninhibited and ethanol-inhibited CoO,Co<Subscript>2</Subscript>O<Subscript>3</Subscript> and Ni<Subscript>2</Subscript>O<Subscript>3</Subscript> catalyzed autoxidation of sulfur(IV) in alkaline medium

For getting an insight into the mechanism of atmospheric autoxidation of sulfur(IV), the kinetics of this autoxidation reaction catalyzed by CoO, Co₂O₃ and Ni₂O₃ in buffered alkaline medium has been studied, and found to be defined by Eqs. I and II for catalysis by cobalt oxides and Ni₂O₃, respectively.

Synthesis,structure, and electric properties of oxygen-deficient perovskites Ba<Subscript>3</Subscript>In<Subscript>2</Subscript>ZrO<Subscript>8</Subscript> and Ba<Subscript>4</Subscript>In<Subscript>2</Subscript>Zr<Subscript>2</Subscript>O<Subscript>11</Subscript>

Perovskite phases Ba₃In₂ZrO₈ and Ba₄In₂Zr₂O₁₁ with the nominal concentration of structural oxygen vacancies 1/9 and 1/12, respectively, were synthesized by solid-phase and solution methods. X-ray diffraction showed cubic symmetry of both phases with the unit cell parameter a = 0.4193(2) and 0.4204(3) nm, respectively. The absence of superstructural lines resulted in the conclusion on statistical arrangement of oxygen vacancies. Thermogravimetry and mass spectrometry proved that both phases can reversibly absorb water from gas phase (pH₂O = 2 × 10⁻² atm) with observed correlation between the concentration of oxygen vacancies and amount of absorbed water. The total water amount was up to 0.9 mol per formula unit or, if recalculated for perovskite unit ABO₃, 0.3 and 0.23 mol H₂O, respectively. The temperature curves of coductivity in the atmosphere with various partial water vapor pressures (pH₂O = 3 × 10⁻⁵ and 2 × 10⁻² atm) showed significantly higher conductivity and lower activation energy (0.52 eV) in humid atmosphere due to proton transfer. The proton conductivity is up to 5 × 10⁻⁴ Ohm⁻¹ cm⁻¹ at 300°C for Ba₃In₂ZrO₈ specimen. IR spectrometry showed that protons in the structure exist primarily in OH-groups.     

Photochemical reactions of <Emphasis Type="Italic">cis</Emphasis>-[(η<Superscript>4</Superscript>-NBD)M(CO)<Subscript>4</Subscript>] (NBD = norbornadiene; M = Cr,Mo) olefin complex with ligand,containing S and N donor atoms

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-[(η⁴-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. The article was submitted by the authors in English.