Lanthanide Complexes with Multidentate Oxime Ligands as Single‐Molecule Magnets and Atmospheric Carbon Dioxide Fixation Systems

The synthesis, structure, and magnetic properties of five lanthanide complexes with multidentate oxime ligands are described. Complexes 1 and 2 ( 1 : [La₂(pop)₂(acac)₄(CH₃OH)], 2 : [Dy₂(pop)(acac)₅]) are synthesized from the 2‐hydroxyimino‐N‐[1‐(2‐pyridyl)ethylidene]propanohydrazone (Hpop) ligand, while 3 , 4 , and 5 ( 3 : [Dy₂(naphthsaoH)₂(acac)₄H(OH)]?0.85 CH₃CN?1.58 H₂O; 4 : [Tb₂(naphthsaoH)₂(acac)₄H(OH)]?0.52 CH₃CN?1.71 H₂O; 5 : [La₆(CO₃)₂(naphthsao)₅ (naphthsaoH)_0.5(acac)₈(CO₃)_0.5(CH₃OH)_2.76H_5.5(H₂O)_1.24]?2.39 CH₃CN?0.12 H₂O) contain 1‐(1‐hydroxynaphthalen‐2‐yl)‐ethanone oxime (naphthsaoH₂). In 1 – 4 , dinuclear [Ln₂] complexes crystallize, whereas hexanuclear La^III complex 5 is formed after fixation of atmospheric carbon dioxide. Dy^III‐based complexes 2 and 3 display single‐molecule‐magnet properties with energy barriers of 27 and 98 K, respectively. The presence of a broad and unsymmetrical relaxation mode observed in the ac susceptibility data for 3 suggest two different dynamics of the magnetization which might be a consequence of independent relaxation processes of the two different Dy³⁺ ions.     

The Model of “Minimal Oscillator” Derived from the Kinetic Mechanism of the H2O2–NaSCN–NaOH–CuSO4 Dynamical System

Dissipative chemical reactions, which involve oscillatory variations of the concentrations of the intermediates in time, are usually characterized with complicated kinetic mechanisms. However, the essential source of the oscillations can often be reduced to only a few reaction steps providing the alternative domination of the positive and negative feedback loops. In an extreme case such a reduction leads to the so–called “minimal oscillator,” the concept used in the past for the well‐known Belousov‐Zhabotinsky (BZ) reaction. In the present work, we construct such a minimal system for the (discovered by M. Orbán) H₂O₂–NaSCN–NaOH–CuSO₄ homogeneous oscillator, in which instabilities originate from kinetic mechanism substantially different from that proposed for the BZ system. The methodology involves intuitive analysis of the reaction mechanism, supported by numerical calculations and spectrophotometric measurements. We show how the actual, only three‐variable model evolves from our previously elaborated: nine‐ and five–variable mechanisms and prove that its further reduction to two–variable one is not possible. Thus the present work is a final step in our searches for the “minimal Orbán oscillator”.     

Synthesis and characterization of metal polycarboxylates constructed from lanthanides(iii) and 1,2,4,5-benzenetetracarboxylic acid

The complexes of yttrium(III) and lanthanides(III) with 1,2,4,5-benzenetetracarboxylic acid were prepared as crystalline solids of the general formula Ln₄(C₁₀H₂O₈)₃⋅14H₂O. They are insoluble in water. On heating in air or inert gas atmosphere all compounds lose water molecules; next anhydrous compounds decompose to oxides. The yttrium complex and heavy lanthanide (from Ho to Lu) ones crystallize in monoclinic crystal system. The dehydration does not change the crystal structure of the compounds.     

Application of fractal geometry for studies of heterogeneity properties of nanomaterials

Calculations based on the fractal geometry in the estimation of surface heterogeneity are superior compared with conventional calculation methods (e.g. from the data of gas adsorption or X-ray radiation scattering) as they can be applied without limitation as far as the range of surface sizes of the studied structures is concerned. This paper presents structural characteristics of carbon and carbon- free nanomaterials based on the determined surface and volumetric fractal coefficients. Fractal coefficients were determined from the data obtained by means of two independent methods: sorptometry and atomic force microscopy (AFM). Correlation between porosity parameters and fractal coefficients is presented.     

Kinetics and Mechanism of Chromium(III)-oxalates-2-hydroxynicotinate and Chromium(III)-oxalates-3-hydroxypicolinate Aquation in HClO4 Solutions

New chromium(III) complexes, [Cr(C₂O₄)₂(2-hnic)]²⁻ and [Cr(C₂O₄)₂(3-hpic)]²⁻ (where 2-hnic = O,O′-bonded 2-hydroxynicotinic acid and 3-hpic = N,O-bonded 3-hydroxypicolinic acid), were obtained and characterized in solution. The acid-catalyzed aquation of the both complexes leads to liberation of the appropriate pyridinecarboxylic acid and formation of cis-[Cr(C₂O₄)₂(H₂O)₂]⁻. Kinetics of these reactions were studied spectrophotometrically in the 0.1–1.0 M HClO₄ range, at I = 1.0 M. In the case of [Cr(C₂O₄)₂(2-hnic)]²⁻, a slow chelate-ring opening at the Cr–O (phenolate) bond is followed by a fast Cr–O (carboxylate) bond breaking. The rate law: k_obs = k_HQ_H[H⁺] was established, where k_H is the acid-catalyzed rate constant and Q_H is the protonation constant of the coordinated phenolate oxygen atom. In the case of [Cr(C₂O₄)₂(3-hpic)]²⁻, the reversible chelate-ring opening at Cr–N bond is followed by the rate determining step – the one-end bonded ligand liberation. The rate law for the first step was determined: k_obs = k₁+k₋₁/Q₁[H⁺], where k₁ and k₋₁ are the rate constants of the chelate-ring opening and closure and Q₁ is the protonation constant of the pyridine nitrogen atom. The aquation mechanisms are proposed and the effect of ligand coordination mode on complex reactivity is discussed.     

Cis-coordination of the chromate anions in helical Co/Ni block-type polymeric systems. Structural and spectroscopic characteristics of catena(μ-CrO4-O,O′)[Co(HIm)3H2O] and catena(μ-CrO4-O,O′)[Co0.43Ni0.57(HIm)3H2O]

Two polymeric complexes: catena(μ-CrO₄-O,O′)[Co(HIm)₃H₂O] (1) and catena(μ-CrO₄-O,O′)[Co_0.43Ni_0.57(HIm)₃H₂O] (2) (where HIm=imidazole) with a cis-bridging coordination mode of the CrO₄ ²⁻ anion have been synthesized and characterized by X-ray and spectroscopic methods. These crystals were isolated from nine systems of varying reagent molar ratios and three excluding anions: Cl⁻, NO₃ ⁻ and SO₄ ²⁻ exclusively as mer [M(HIm)₃O₃]-type isomers. The unit cell of these isostructural complexes (monoclinic crystal system P2₁ /n) contains two independent helixes, left- and right handed, stabilized by intrahelical and interhelical hydrogen bonding and π–π interaction between pairs of the imidazole rings from neighbouring helixes. The Raman spectra at 77 K of 1 and 2 deconvoluted into lorentzian components revealed the block-type polymeric structure of the complexes. Moreover, the solution studies at millimolar concentrations of 1 and 2 indicated their complete decomposition in water. Four K electronic spectral analysis of the crystals (band deconvolution into gaussian components) enhanced with the data obtained in the polarized light allowed for assignment of the bands to the respective d–d transition (D_4h symmetry). It was found that the metallic centres are independently absorbing species, which supports the suggestion of a block-type structure of the polymers. The respective crystal field parameters for Co and Ni were calculated.     

Chemistry of palladium phosphinite (PPh(2)(OR)) and phosphonite (P(OPh)(2)(OH)) complexes: catalytic activity in methoxycarbonylation and Heck coupling reactions

The new phosphinite and phosphonite complexes (1-8) are very efficient catalysts for the methoxycarbonylation of iodobenzene and Heck cross-coupling of bromobenzene with butyl acrylate. High catalytic activity of these complexes can be explained by their in situ transformations during the reaction, stimulated by the presence of water, acid (HCl) or base (NEt(3)). Hydrolysis of phosphinite palladium complexes of the form trans-PdCl(2)[PPh(2)(OR)](2) (R = C(6)F(5), 2, (t)Bu 3, or O-menthyl 4) results in the formation of the dimeric complex [mu-ClPd(PPh(2)OH)(PPh(2)O)](2) 5, which is deprotonated by NEt(3), producing a polymeric complex of formula [Pd(P(O)PPh(2))(2)](n) 8. The reverse reaction, protonolysis of 8 with HCl, leads back to 5 and the monomeric complex 5a. The phosphinite complex PdCl(2)[PPh(2)(OBu)](2)1 with a more lipophilic ligand, PPh(2)(OBu), does not undergo hydrolysis under the same conditions. In the reaction of PdCl(2)(cod) with P(OPh)(2)(OH), the new dimer [mu-ClPd(P(OPh)(2)OH)(P(OPh)(2)O)](2) 6 was obtained, whereas reaction of Pd(OAc)(2) with P(OPh)(2)(OH) leads to the polymeric complex [Pd[P(O)(OPh)(2)](2)](n) 7. Protonolysis of 7 with HCl results in the formation of 6.     

Chemical potential of a hard sphere fluid adsorbed in model disordered polydisperse matrices

We consider a model for adsorption of a simple fluid in disordered polydisperse adsorbents. The fluid consists of hard sphere particles. On the other hand, the adsorbents of this study are modeled as a collection of hard spheres with their diameter obeying a certain distribution function. Our focus is in the evaluation of the chemical potential of the fluid immersed in such a polydisperse material. It permits us to obtain porosity and pore size distribution for the adsorbent, as well as a set of adsorption isotherms. The latter have been calculated theoretically and by grand canonical Monte Carlo simulations. We observe that the width of assumed polydispersity distribution affects all the properties of the system. Nevertheless, the effect of matrix packing is dominant in determining adsorption for this class of models. We are convinced that the matrix structures generated via more sophisticated algorithms would exhibit stronger effects of polydispersity on the entire set of properties of adsorbed simple fluids.     

A simple and practical phase-separation approach to the recycling of a homogeneous metathesis catalyst

The air stable asarone-derived Ru carbene 16, a robust olefin metathesis catalyst, can be easily separated after reaction by deposition on silica gel and reused up to nine times. This procedure provides products of excellent purity with low Ru content.     

Studies of heterogeneity properties of selected high-temperature superconductor surfaces

Nitrogen adsorption measured at 77 K was used to characterize the surface heterogeneity of high-temperature superconductor surfaces. Properties relating to adsorption and porosity of the solids (adsorption capacity, specific surface area, radii and volume of the pores, pore-size distribution function) were determined from nitrogen adsorption–desorption isotherms and atomic force microscopy (AFM) for a series of oxide superconductors. It is shown that the adsorption isotherms of all samples are S-shaped and belong to type II according to the IUPAC classification. On the basis of the nitrogen adsorption isotherms and AFM data, fractal dimensions were determined and correlations found with adsorption and porosity parameters.