Phosphorus-containing podands 7. Complexing properties of ortho-diphenylphosphinyl-substituted diphenyl ethers of oligoethylene glycols with respect to alkali-metal cations

Stability constants of complexes of alkali-metal cations with oligoethylene glycol diethers RO(CH₂CH₂O)_nR (n=1–5), where R=2-Ph₂P(O)C₆H₄ and 2-Ph₂(O)-4-t-BuC₆H₃P, have been determined conductometrically in a tetrahydrofuran-chloroform mixture (41 by volume). The dependence of complexing ability on a number of monopodand donor centers for Li⁺ and Na⁺ has multiple extrema. For K⁺, Rb⁺, and Cs⁺ the complexing abilities steadily increase with the length of the ligand polyether chain. Monopodands based on triethylene glycol and its pyrocatechol analog are highly effective (log K=6.7–7.0) with respect to Li⁺. The synthesis of ligands with a lipophilic tert-butyl substituent in the terminal group is described.For previous communication, see [1]. The number of the communication in [2] is 5, not 4 as printed in error.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 1992–2000, September, 1991.     

The number of propagating species and some rate constants of elementary acts for the polymerization of ethylene and α-olefins using supported Ziegler catalysts

Concentrations of propagating species (PS) and chain propagation constants (k_p) were determined for the polymerizations of ethylene, propylene, butene-1 and hexene-1 using TiCl₄/MgO-Al(C₂H₅)₃ (i) and TiCl₄/Al₂O₃. SiO₂-Al(C₂H₅)₃ (II) catalytic systems. The concentrations of propagating species for all monomers and a particular catalytic system are close. They give an idea of high degree of application of transition metal ($\text{? 35–39\%}$ of total Ti for system I and $\text{? 20–23\%}$ for system II). Values of k_p for ethylene, propylene, butene-1, hexene-1 at 70° for system I are 2440 ± 240, 4.8 ± 0.5, 4.6 ± 0.5 and 2.5 ± 0.3 l/mol·sec respectively. For system II, k_p values for the first three monomers are 110 ± 11, 1.0 ± 0.1 and 0.13 ± 0.01 l/mol·sec. These results indicate the relation of reactivity of propagating species and chemical nature of the support to the surface of which they are fixed. Rate constants for chain transfer to monomer or triethyl aluminium and spontaneous disproportionation (at 70°) were compard for the polymerizations of ethylene and propylene using catalytic system I.     

Effect of Phosphonium Ionic Liquids on the Extraction of Rare-Earth Elements(III) with 2,2′-Oxybis(N,N-dioctylacetamide) from Nitric Acid Solutions

Russian Journal of General Chemistry - New phosphonium ionic liquids, alkyldiphenylethylphosphonium bis[(trifluoromethyl)sulfonyl]imides (Alk = C4H9, C8H17, and C12H25) have been synthesized. The...     

Ion-selective and complexation properties, vibrational spectra, and crystal and molecular structure of 1,5-bis[2-(hydroxyethoxyphosphoryl)phenoxy]-3-oxapentane

The ion-selective properties of 1,5-bis[2-(hydroxyethoxyphosphoryl)phenoxy]-3-oxapentane H₂R² have been described. The molecular and crystal structure of H₂R² has been determined by powder X-ray crystallography and IR spectroscopy. The molecule has the twofold symmetry axis, orthorhombic crystal system, space group Pbcn, a = 16.830(2) ?, b = 8.866(15) ?, c = 15.7190(2) ?, V = 2346.1(6) ?³, Z = 4. A new CuR² · 2H₂O complex has been synthesized and characterized.     

Complex-forming and ion-selective properties of bis(2-diphenylphosphorylalkyl)phenyl ethers of ethylene glycols. Crystal structures of cadmium complexes

New complexes of cadmium iodide with 1,3-bis[2-(diphenylphosphoryl)phenoxy]propane [CdL⁰I₂], 1,2-bis[2-(diphenylphosphorylethyl)phenoxy]ethane [CdL^{1, 2}I₂], and 1,8-bis[2-(diphenylphosphorylethyl) phenoxy]-3,6-dioxaoctane [CdL^{3, 2}I₂] are synthesized and their IR spectra and crystal structures are studied. Electroanalytical characteristics of membranes of ion-selective electrodes based on L⁰, L^{1, 2}, L^{3, 2}, and known crown ethers are compared for cations of alkali, alkaline-earth, and transition metals. Ligand L^{3, 2} is the first podand with terminal diphenylphosphoryl fragments to exhibit selectivity with respect to the cadmium cation.     

Higher order symmetrizer and application to an unusual transport equation

We study a class of stationary transport equation with nonlocal low-order tems We obtain the existence and uniqueness of a solution in sobolev spaces     

Evaluation of Applicability of Aminodiphosphonic Acids for the Development of Bone-Seeking 68Ga-Radiopharmaceuticals

Russian Journal of General Chemistry - The binding of 68Ga to two organic ligands containing aminodiphosphonic groups (1,7-diamino-4-oxaheptane-1,1,7,7-tetraphosphonic and...     

2,5-Diamino-5,5-diphosphonovaleric Acid as a Ligand for an Osteotropic <Superscript>188</Superscript>Re Radiopharmaceutical

A modified method for the preparation of 2,5-diamino-5,5-diphosphonovaleric acid (DADP5) has been developed in the search for new synthetically available organic ligands to produce ¹⁸⁸Re radiopharmaceuticals with an increased accumulation in the bone tissue. Interaction of the obtained acid with ¹⁸⁸Re was studied by radio-TLC. An optimal system for separating unbound ¹⁸⁸Re and labeled complex in a yield of at least 95% was found. The biological distribution of ¹⁸⁸Re-DADP5 was studied based on direct radiometric data. The osteotropicity of ¹⁸⁸Re-DADP5 and its increased accumulation in bone fracture sites, which represent oncological pathology models, was detected at a level comparable to known radiopharmaceuticals.     

Synthesis and vibrational spectra of copper(II) and erbium(III) complexes with 2-[2′-(oxymethyldiphenylphosphinyl)phenyldiazenyl]-4- tert -butylphenol (HL) [CuL2] · 2H2O and Er(NO3)2 · 2 HL · 2H2O. Crystal structure of [CuL2] · 2H2O

The syntheses of the complex copper salt CuL₂ · 2H₂O (I) and the erbium nitrate complex Er(NO₃)₃ · 2HL · 2H₂O (II) (HL is 2-[2′-(oxymethyldiphenylphosphinyl)phenyldiazenyl]-4-tert-butylphenol) have been described. Basic vibrational frequencies in the IR spectra of I and II have been interpreted. The crystal structure of I has been determined by X-ray crystallography: the crystals are monoclinic, a = 15.157(3) ?, b = 17.080(2) ?, c = 22.451(9) ?, β = 106.09(3)°, V = 5584(3) ?³, Z = 4, space group C2/c, R = 0.0546 (for 1152 reflections with I > 2σ(I)). The coordination polyhedron of the copper atom (symmetry C ₂) can be described as a symmetrically elongated square bipyramid (4+2). The basic square of the Cu polyhedron is formed by the oxygen atom of the substituted phenol and one of the nitrogen atoms of the azo group of each of the two deprotonated ligands L⁻ (Cu-N, 1.969(6) ?; Cu-O, 1.899(5) ?). The angles between the opposite O and N atoms are 157.6°, and the other equatorial angles are in the range 90.6°–95.9°. The axial positions are occupied by the anisole O(2) and O(2A) atoms (Cu-O, 2.737(6) ?, the O(2)Cu(1)O(2A) angle, 132.3°). In the crystal of I, complex molecules and water molecules of crystallization are combined by a system of hydrogen bonds. IR spectra show that, in complex II, as distinct from compound I, the HL ligand is coordinated to the erbium atom through the phosphoryl oxygen atom. Original Russian Text ? A.Yu. Tsivadze, L.Kh. Minacheva, I.S. Ivanova, V.E. Baulin, E.N. Pyatova, V.S. Sergienko, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 4, pp. 601–607.