Complexes of crown-containing N-thioacylamido(thio)phosphates with Zn(II) and Co(II) cations

Reaction of the potassium salts of N-acylamido(thio)phosphates [4′-benzo-15-crown-5]NHC(S)NHP(Y)(OiPr)2 (Y = S, HLI; Y = O, HLII) with Zn(II) and Co(II) cations in aqueous EtOH leads to complexes of formulae Zn(LI,II - S,Y)2 (Y = S, 1; Y = O, 2) and Co(LI-S,S′)2 (3), while interaction of the potassium salt of [4′-benzo-15-crown-5]C(S)NHP(O)(OiPr)2 (HLIII) with Zn(II) in the same conditions leads to a complex of composition Zn(HLIII)(LIII-S,O)2 (4). © 2006 Elsevier B.V. All rights reserved

Nitrocellulose membrane, modified by RC(S)NHP(X)(OiPr)2 (X = S, R = PhNH; X = O, R = PhNH, Ph), for sorption extraction of cobalt cations

The complexation and extraction properties of RC(S)NHP(X)(OiPr)2 [X = S, R = PhNH (HLI); X = O, R = PhNH (HLII), Ph (HLIII)] towards cobalt cations were studied. The nitrocellulose membrane was used as a carrier for HLI-III. The maximal degree of extraction of cobalt cations from an aqueous solution is observed at pH = 7.8-8.4. It was established that complexes formed are kept in a water solution on a surface of the carrier and washed away in 96% aqueous ethanol. The membrane modified by HLI allows extraction and concentration of Co(II) selectively, while the modification by HLIII leads to the selective extraction of Co(III). Copyright © 2010 Taylor & Francis Group, LLC

Complexes of N-thiophosphorylthioureas RNHC(S)NHP(S)(OiPr)2 (HL) (R = pyridin-2-yl, pyridin-3-yl, 6-amino-pyridin-2-yl) with copper(I): Crystal structures of Cu(PPh3)nL (n = 1, 2)

Reaction of the potassium salts of N-thiophosphorylated thioureas of common formula RNHC(S)NHP(S)(OiPr)2 [R = pyridin-2-yl (HLa), pyridin-3-yl (HLb), 6-amino-pyridin-2-yl (HLc)] with Cu(PPh3)3I in aqueous EtOH/CH2Cl2 leads to mononuclear [Cu(PPh3)2La,b-S,S′] (1, 2) and [Cu(PPh3)Lc-S,S′] (3) complexes. Using copper(I) iodide instead of Cu(PPh3)3I, polynuclear complexes [Cun(L-S,S′)n] (4-6) were obtained. The structures of these compounds were investigated by IR, 1H, 31P{1H} NMR spectroscopy, ES-MS and elemental analyses. The crystal structures of Cu(PPh3)2Lb (2) and Cu(PPh3)Lc (3) were determined by single-crystal X-ray diffraction. © 2008 Elsevier B.V. All rights reserved

New bifunctional N-thiophosphorylated thiourea and 2,5-dithiobiurea derivatives. Crystal structures of R[C(S)NHP(S)(OiPr)2]2 (R = -N(Ph)CH2CH2N(Ph)- and -NHNH-)

A new bifunctional N-thiophosphorylated thiourea and 2,5-dithiobiurea of the common formula R[C(S)NHP(S)(OiPr)2]2 [R = -N(Ph)CH2CH2N(Ph)- (H2La); -NHNH- (H2Lb)] have been synthesized and characterized by IR, 1H, 31P spectroscopy and the single crystal X-ray diffraction method. The structure of the latter compound in CDCl3 and acetone-d6 solutions has been discussed in comparison with the monofunctional thiosemicarbazide PhNHNHC(S)NHP(S)(OiPr)2 (HLc). © 2008 Elsevier Ltd. All rights reserved

Ethnodemography of Bashkirs in Regions of Russia (1970—2010)

The issues of ethno-demographic and ethno-linguistic development of the Bashkir population in the regions of the Russian Federation are considered. It is noted that the tendencies of demographic processes among the Bashkirs in the regions and in the republic of the same name are very different. The features of the ethnodemographic development of the Bashkirs in the regions of their historical settlement are shown, in which general trends coincide with the demographic processes in the country as a whole. It cannot be said about the Republic of Bashkortostan, which is characterized by sharp fluctuations in the size of the titular ethnic group. The dynamics of the ethnic and linguistic identity of the Bashkir population in the regions of historical settlement is revealed in a comparative aspect with the subjects to which the Bashkirs moved at a later time and in which their number is a small proportion. The novelty of the study lies in the fact that it was the first to analyze the ethno-demographic and ethno-linguistic aspects of the development of the Bashkirs in the Russian Federation, including in the regions of their historical settlement. The relevance of the study is due to the fact that the issue of the demographic development of the Bashkir population at the present stage, especially in the republic of the same name, has acquired an ethnopolitical discourse. It has been proven that, despite the policy of reviving ethnicity and the native language, the Bashkirs, like other peoples, are gradually losing it in favor of being recognized as a native Russian

Complexes of crown ether-containing N-phosphorylated thioamides and thioureas with CoII, ZnII and PdII cations

The reaction of the potassium salts of N-phosphorylated thioureas [4'-benzo-15-crown-5]NHC(S)NHP(Y)(OiPr)2 (Y = S, HLI; Y = O, HLII) with ZnII and CoII cations in aqueous EtOH leads to complexes of formulae Zn(LI,IIS,Y)2 (Y = S, 1; Y = O, 2) and Co(LIS,S')2 (3), while interaction of the potassium salt of N-phosphorylated thioamide [4'-benzo-l5-crown-5]C(S)NHP(O) (OiPr)2 (HLIII) with ZnII in the same conditions leads to the complex Zn(HLIII)(LIII-S,O) 2 (4). The reaction of the potassium salt of crown ether-containing N-phosphorylated bis-thiourea N,N'-[C(S)NHP(O)(OiPT)2] 2-1,10-diaza-18crown-6 (H2L) with CoII, Zn.II and PdII cations in anhydrous CH3OH leads to complexes M2(L-O,A)2 (M = Co, 5; Zn, 6; M = Pd, 7). Thioamide HLIII was investigated by single-crystal X-ray diffraction. © 2009 Wiley-VCH Verlag GmbH & Co. KGaA

Complexes of a novel N-(diisopropxythiophosphoryl)thiourea derivative of 1,4,8,11-tetraazacyclotetradecane with Na+, K+ and Cu (PPh3)2 + cations

The reaction between 1,4,8,11-tetraazacyclotetradecane (cyclam) and O,O′-diisopropyl-isothiocyanatothiophosphoric acid (iPrO)2P(S)NCS gives the tetra-functional thiourea H4L with four C(S)NHP(S)(OPri)2 groups attached to the intracyclic nitrogen atoms. The tetra-substituted product has been obtained in the solid state, while partial dissociation with elimination of isothiocyanate (iPrO)2P(S)NCS takes place in CCl4 and CDCl3 solutions. Deprotonation of the exocyclic groups prevents the dissociation, and alkali metal salts of M4L formula (M = Na+, K+) were obtained by treatment with MOH. The potassium salt K4L was used to synthesize the Cu(I) complex [{Cu(PPh3)2}4L] by reaction with Cu(PPh3)3I. © 2006 Elsevier Ltd. All rights reserved

Intramolecular hydrogen bond controlled monodentate S-coordination of N-phosphoryl-N′-(R)-thioureas with Pd(II)

Reaction of N-phosphorylated thioureas RNHC(S)NHP(O)(OiPr)2 (R = tBu, HLI; R = Ph, HLII; R = 4′-benzo-15-crown-5, HLIII) with Pd(PhCN)2Cl2 in acetonitrile leads to complexes of formulae Pd(HLI-S)2Cl2 (1), Pd(HLII-S)2Cl2 (2) and Pd(HLIII-S)2Cl2 (3). The crystal structure of complex 1 has been investigated by X-ray crystallography. It was established that the thiourea ligands are in a trans-configuration and the palladium(II) cation is coordinated by the sulfur atoms of the C{double bond, long}S groups and the chlorine atoms. Complex 1 is the first example of palladium(II) complex in which the potentially chelating N-phosphorylated thiourea ligand is bound through the sulfur atom only. © 2008 Elsevier B.V. All rights reserved

Novel bicyclic hexanuclear copper(I) aggregate: Structure and solid state 31P CPMAS NMR spectra of [(Cu3L3)2] and [Cu(PPh3)2L] complexes of N-(diisopropoxythiophosphinyl)-N′-phenylthiourea (HL)

A new complex of N-thiophosphorylthiourea PhNHC(S)NHP(S)(OiPr)2 (HL) of formula [(Cu3L3)2] has been synthesized and characterized by single crystal X-ray diffraction, FT-IR, 1H, 31P NMR in solution and by 31P CPMAS NMR spectroscopy in the solid state. A comparison of the structure and the spectral parameters of [(Cu3L3)2] with those of the mononuclear analogue [Cu(PPh3)2L] was performed. In the solid state the aggregate [(Cu3L3)2] represents the first example of a spontaneous "side-by-side" association of two neutral cyclic [Cu3L3] moieties using two Cu-S-Cu bridges formed by the sulfur atoms of the PS-groups. The values of the 1J(31P-63,65Cu) and 2J(31P-31P) coupling constants of the [Cu(PPh3)2]+ moiety in the solid state spectra are reported. © 2008 Elsevier B.V. All rights reserved

Complexes of N-thiophosphorylthiourea α-naphthylnhc(S)NHP(S)(OiPr)2 (HL) with copper(I). crystal structures of HL and Cu(PPh3)2L

Reaction of the potassium salt of N-thiophosphorylated thiourea α-naphthylNHC(S)NHP(S)(OiPr)2 (HL) with Cu(PPh3)3I in aqueous EtOH/CH2Cl2 leads to the mononuclear complex [Cu(PPh3)2L-S,S′]. By using copper(I) iodide instead of Cu(PPli3)3I, the polynuclear complex [Cun(L-S,S′)n was obtained. The structures of these compounds were investigated by elemental analysis, H and 31P{1H} NMR and IR spectroscopy. The crystal structures of HL and Cu(PPh3)2-L were determined by singlecrystal X-ray diffraction. © 2009 Wiley-VCH Verlag GmbH & Co. KGaA