Search

© Pleiades Publishing, Ltd., 2014. Structure and intramolecular transformations of N-phenyl,N'-(diisopropoxythiophosphoryl)thiourea has been studied by NMR spectroscopy and the AM1 quantum-chemical simulation. It has been shown that several forms, including two amide forms (EZ and ZE) and two prototropic forms, coexist in a dynamic equilibrium.

N-(Thio)phosphorylated (thio)carbamides and (thi o)amides are proposed as modifiers of polymer nitrocellulose membranes for the adsorption preconcentration of Ni(II), Zn(II), and Cd(II) from aqueous solutions. The binding constants of metalions with the immobilized reagents are 1.5-2.5 times higher than those with monomer ligands in solution. The preconcentration coefficients are 1950-3500. Aprocedure was developed for the adsorption preconcentration and recovery of Ni(II), Zn(II), and Cd(II) as complex compounds, using nitrocellulose membranes modified with N-(thio)phosphorylated thiocarbamides and thioamides. © 2010 Pleiades Publishing, Ltd.

Reaction of O,O'-diisopropylthiophosphoric acid isothiocyanate (iPrO) 2P(S)NCS with 1,10-diaza-18-crown-6, 1,7-diaza-18-crown-6, or 1,7-diaza-15-crown-5 leads to the N-thiophosphorylated bis-thioureas N,N'-bis[C(S)NHP(S)(OiPr)2]-1,10-diaza-18-crown-6 (H 2LI), N,N'-bis[C(S)NHP(S)(OiPr)2]-1,7-diaza-18- crown-6 (H2LII) and N,N'-bis[C(S)NHP(S)(OiPr) 2]-1,7-diaza-15-crown-5 (H2LIII). Reaction of the potassium salts of H2LI-III with a mixture of CuI and 2,2'-bipyridine (bpy) or 1,10-phenanthroline (phen) in aqueous EtOH/CH 2Cl2 leads to the dinuclear complexes [Cu 2(bpy)2LI-III] and [Cu2(phen) 2LI-III]. The structures of these compounds were investigated by 1H, 31P{1H} NMR spectroscopy, and elemental analysis. The crystal structures of H2LI and [Cu2(phen)2LI] were determined by single-crystal X-ray diffraction. Extraction capacities of the obtained compounds in comparison to the related compounds 1,10-diaza-18-crown-6, N,N'-bis[C(=CMe2)CH2P(O)(OiPr)2]-1,10-diaza-18- crown-6, N,N'-bis[C(S)NHP(O)(OiPr)2]-1,10-diaza-18-crown-6 towards the picrate salts LiPic, NaPic, KPic. and NH4Pic were also studied. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

Reaction of the lithium salt of N-phosphorylated thiourea [4′-benzo-15-crown-5]NHC(S)NHP(O)(OiPr)2 (HLI) with NiII leads to the chelate complex [NiLI 2]. The metal center is found in a square-planar N2S2 environment formed by the CS sulfur atoms and the P-N nitrogen atoms of two deprotonated LI ligands. Reaction of [NiLI 2] and its non-crown ether-containing analog Ni[PhNHC(S)NP(O)(OiPr)2] 2 ([NiLII 2]) with 2,2′-bipyridine (bipy) and 1,10-phenanthroline (phen) leads to the [Ni(bipy)LI,II 2] and [Ni(phen)LI,II 2] heteroligand complexes. The coordination mode is preserved for the phosphorus-containing ligands. The extraction properties of the crown ether-containing compounds towards alkali metal picrates were investigated. The molecular structures of HLI, [NiLI 2] and [Ni(bipy)LII 2] were elucidated by X-ray diffraction. © 2009 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.

Structure and intramolecular transformations of N3-phenyl-N 1-(diisopropoxythiophosphoryl)-thiosemicarbazide in CD 2Cl2 were studied by one- and two-dimensional 1H, 13C and 31P NMR spectroscopy. The combined analysis of the data of NMR spectroscopy and calculation simulation confirmed a high lability of the studied compounds resulting in the formation of various conformational and tautomeric forms in solutions. The preference of Z,E-conformation of the amide form with cis- and trans-location of two N-H groups and the C=S group relatively to the two C-N bonds was revealed. © 2009 Pleiades Publishing, Ltd.

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.

The photoluminescent properties of 17 zinc(II) chelates [Zn(RC(S)NP(O)(OiPr)2-O,S)2] (R = Ph (1a), PhNH (1b), p-BrPh (1c), p-MeOC6H4NH (1d), p-BrC6H4NH (1e), NH2 (1f), iPrNH (1g), tBuNH (1h), Et2N (1i), c-C5H10N (1j), c-OC4H8N (1k), c-C6H11NH (1l), aminobenzo-15-crown-5 (1m)) and [Zn(B)(RC(S)NP(O)(OiPr)2-O,S)2] (R = Ph, B = 2,2′-bipyridine (2a); R = Ph, B = 1,10-phenanthroline (2b); R = PhNH, B = 2,2′-bipyridine (2c); R = PhNH, B = 1,10-phenanthroline (2d)), are reported. Colorless and air/moisture stable chelate complexes of divalent zinc show blue emission in the solid state when excited with UV light. Complexes 1f, 1h, 1l were investigated by single crystal X-ray diffraction. The zinc(II) atom in complexes 1f, 1h, 1l is in a distorted tetrahedral O2S2 environment formed by the C{double bond, long}S sulphur atoms and the P{double bond, long}O oxygen atoms of two deprotonated ligands. © 2008 Elsevier Ltd. All rights reserved.

Reaction of N-phosphorylated thioureas of common formula 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 the structure Pd(HLI-S)2Cl2 (1), Pd(HLII-S)2Cl2 (2) and Pd(HLIII-S)2Cl2 (3). Reaction of N-phosphorylated thioureas of common formula RC(S)NHP(O)(OiPr)2 (R = Et2N, HLIV; R = morpholine-N-yl, HLV) in the same conditions leads to complexes Pd(LIV-O,S)2 (4) and Pd(LV-O,S)2 (5), where the palladium(II) atoms are coordinated in a square-planar fashion by the C{double bond, long}S sulfur atoms and the P{double bond, long}O oxygen atoms of two anionic ligands. 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 Ltd. All rights reserved.

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.

Reaction of the potassium salt of N-diisopropoxyphosphinyl-p- bromothiobenzamide p-BrC6H4C(S)NHP(O)(OiPr)2 (HL) with Ni(NO3)2 in aqueous EtOH leads to complex of formula [Ni(HL-O)2(L-O,S)2] (1). The structure of 1 was investigated by single crystal X-ray diffraction analysis, IR, 1H and 31P{1H} NMR spectroscopy, MALDI and microanalysis. The nickel(II) ion in 1 has a tetragonal-bipyramidal environment, (O ax)2(Oeq)2(Seq) 2, with two neutral ligand molecules coordinated in axial positions through the oxygen atoms of the P=O groups. The equatorial plane of bipyramide is formed by two anionic ligands involving 1,5-O,S-coordination mode. The chelating ligands are bound in trans configuration. © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.

Reaction of the potassium salt of N-thiophosphorylthiourea tBuNHC(S)NHP(S)(OiPr)2 (HL) with ZnII, CdII, NiII and CoII in aqueous EtOH leads to complexes of common formula M(L-S,S′)2 (ML2). Complexes were investigated by IR, UV-Vis, 1H and 31P{1H} NMR spectroscopy and microanalysis The structure of complex NiL2 was investigated by single crystal X-ray diffraction analysis. The nickel(II) ion has a squre-planar environment, S4, with two anionic ligands involving 1,5-S,S′-coordination mode. The ligands are bound in a trans configuration. © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.

The behavior of ambidentate organophosphorus ligands is of general interest because the nature of the phosphorus-element bond influences directly on the structure of chelate complexes of these compounds. Reasons allowing the polyfunctional ligands to bind metal cations using different coordination modes, closely address the fundamental questions of chemistry, such as the nature of chemical bonding and the isomerism of coordination compounds, or the influence of the ligand structure on regioselectivity of the coordination bond formation and definition of a role of weak intramolecular interactions in the structure stabilization. In the framework of the presented review the information about ambidentate coordination properties of N-Thiophosphorylated thioamides, thioureas of common formula RC(X)NHP(Y)R'2 towards VIIIB group metal cations Co(II), Ni(II), Pt(II) and Pd(II) were summarized and discussed in comparison with organic and diphosphorus analogues: (i) N-acylamides and ureas of common formula RC(X)NHC(Y)R' (NAAU), and (ii) dichalcogenoimididiphosphinates R2P(X)NHP(Y)R'2 (IDP) (X, Y = O, S, Se).© 2008 by Nova Science Publishers, Inc. All rights reserved.

The reaction of the potassium salts of N-(thio)phosphorylated thioureas of the common formula AdN(H)C(S)N(H)P(X)(OiPr)2 (X = O, HLI; X = S, HLII) with the Ni(II) cation in aqueous EtOH leads to [Ni(LI,II)2] chelate complexes. The molecular structures of the thioureas HLI,II and the complexes [Ni(LI-N,S)2] and [Ni(LII-S,S′)2] were elucidated by single crystal X-ray diffraction analysis, IR, 1H and 31P NMR spectroscopy and microanalysis. In the complex [Ni(LI)2], the metal center is found to be in a square-planar N2S2 environment formed by the C{double bond, long}S sulfur atoms and the P-N nitrogen atoms of two deprotonated LI ligands. The ligands are in a trans configuration. The Ni(II) atom in complex [Ni(LII)2], with the deprotonated thiourea LII, is coordinated in a square-planar fashion by the C{double bond, long}S and P{double bond, long}S sulfur atoms of two anionic ligands. The ligands are in a cis configuration. © 2008 Elsevier Ltd. All rights reserved.

The title complex has been studied by 1H and 31P NMR spectroscopy and found to undergo reversible dissociation of its neutral ligands and interconversion of its neutral and anionic ligands; the kinetic parameters of these processes and the crystal structure of the complex were determined; a new ligand exchange mechanism with unusual high spin-low spin transition during the ligand dissociation was suggested. © 2008.

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.

Structure and magnetic properties of CoII complexes with N-phosphorylthiourea derivatives [RC(S)NHP(O)(OiPr)2] (HL) [Co {Et2NC(S)NP(O)(OzPr)2}2] (1), [Co [(PrNHC(S)NP(O)-(OiPr)2}2] (2), [Co {[/BuNHC(S)NP(O)(OiPr) 2}2] (3), [Co{p-MeOC6H4NHC(S)NP(O) (O(Pr)2}2] (4), [Co{P-BrC6H4NHC-(S) NP(O)(O(Pr)2}2] (5) were investigated. Paramagnetic shifts in the 1H NMR spectrum were observed for high-spin CoII complexes with HL, incorporating amidophosphate moiety C(S)NP(O). The thermal dependence of the magnetic susceptibility has shown that the extended materials 2, 3 and 5 show ferromagnetic exchange between distorted tetrahedral metal atoms, while in complex 4 antiferromagnetic behavior takes place. Compound 1 behaves as a spincanted ferromagnet, an antiferromagnetic ordering taking place below a critical temperature, Tc = 175 K. Complex 2 was investigated by single crystal X-ray diffraction. The cobalt(II) atom in complex 2 is in distorted tetrahedral CoO2S2 environment formed by the C=S sulfur atoms and the P=O oxygen atoms of two deprotonated ligands. © 2007 WILEY-VCH Verlag GmbH & Co. KGaA.

The acid-base and coordination properties of N-(thio)phosphorylated thioureas and thioamides R1C(X)NHP(Y)R 2 2, where X, Y = S, O (in various combinations); R1 = t-Bu, i-Pr, PhNH, Ph; R2 = (OPr-i), with respect to Co(II), Ni(II), Zn(II), and Cd(II) ions have been studied by pH-metry and UV spectrometry in an organic solvent. The pK values, the stability constants logβ and the maximum accumulated fractions of complex species in the solution have been calculated. © 2007 Pleiades Publishing, Inc.

For N-(thio)phosphorylthioureas of the common formula RC(S)NHP(X)(OiPr)2 HLI (R = N-(4′-aminobenzo-15-crown-5), X = S), HLII (R = N-(4′-aminobenzo-15-crown-5), X = O), HLIII (R = PhNH, X = S), HLIV (R = PhNH, X = O), and (N,N′-bis-[C(S)NHP(S)(OiPr)2]2-1,10-diaza-18-crown-6) H2LV, salts LiLI,III,IV, NaLI-IV, KLI-IV M2LV (M = Li+, Na+, K+), Ba(LI,III,IV)2, and BaLV have been synthesized and investigated. Compounds NaLI,II quantitatively drop out as a deposit in ethanol medium, allowing the separation of Na+ and K+ cations. This effect is not displayed for the other compounds. The crystal structures of HLIII and the solvate of the composition [K(Me2CO)LIII] have been investigated by X-ray crystallography. © 2006 Elsevier Ltd. All rights reserved.

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.

Structure and magnetic properties of N-diisopropoxyphosphorylthiobenzamide PhC(S)-N(H)-P(O)(OiPr) 2 (HL I) and N- diisopropoxyphosphoryl-N′-phenylthiocarbamide PhN(H)-C(S)-N(H)-P(O)(OiPr) 2 (HL II) complexes with the Co II cation of formulas [Co {PhC(S)-N-P(O)(OiPr) 2} 2] (1), [Co(PhN(H)-C(S)-N-P(O)(OiPr) 2] 2] (2), [Co{PhC(S)-N(H)-P(O) (OiPr) 2} 2{PhC(S)-N-P(O)(OiPr) 2} 2] (1a) and [Co{PhC(S)-N-P(O)(OiPr) 2} 2}(2,2′-bipy)] (3), [Co{PhC(S)-N-P(O)(OiPr) 2} 2(1,10-phen)] (4), [Co{PhN(H)-C(S)-N-P(O)(OiPr) 2] 2(2,2′-bipy)] (5), [Co(PhN(H)-C(S)-N-P(O)(OiPr) 2} 2(1,10-phen)] (6) were investigated. Paramagnetic shifts in the 1H NMR spectrum were observed for high-spin Co II complexes with HL I,II, incorporating the S-C-N-P-O chelate moiety and two aromatic chelate ligands. Investigation of the thermal dependence of the magnetic susceptibility has shown that the extended materials 1-2 and 6 show ferromagnetic exchange between distorted tetrahedral (1, 2) or octahedral (la, 6) metal atoms whereas 3 and 5 show antiferromagnetic properties. Compound 4 behaves as a spin-canted ferromagnet, an antiferromagnetic ordering taking place below a critical temperature, T c = 115 K. Complexes 1 and 1a were investigated by single crystal X-ray diffraction. The cobalt(II) atom in complex 1 resides a distorted tetrahedral O 2S 2 environment formed by the C=S sulfur atoms and the P=O oxygen atoms of two deprotonated ligands. Complex la has a tetragonal-bipyramidal structure, Co(O ax) 2(O eq) 2(S eq) 2, and two neutral ligand molecules are coordinated in the axial positions through the oxygen atoms of the P=O groups. The base of the bipyramid is formed by two anionic ligands in the typical 1,5-O,S coordination mode. The ligands are in a trans configuration. © 2007 WILEY-VCH Verlag GmbH & Co. KGaA.

Reaction of the potassium salts of N-thiophosphorylated thioureas of common formula RC(S)NHP(S)(OiPr)2 [R = morpholin-N-yl (HLa), piperidin-N-yl (HLb), NH2 (HLc), PhCH 2NH (HLd)] with Cu(PPh3)3I in aqueous EtOH/CH2Cl2 leads to mononuclear [Cu(PPh 3)2L-S,S′] complexes. Using copper(i) iodide instead of Cu(PPh3)3I, polynuclear complexes [Cu n(L-S,S′)n] were obtained. The structures of these compounds were investigated by ES-MS, elemental analyses, 1H and 31P NMR in solution, IR and 31P solid-state MAS NMR spectroscopy. The crystal structures of [Cu3L3 a] and [Cu(PPh3)2Lb] were determined by single-crystal X-ray diffraction. © The Royal Society of Chemistry 2007.

Reaction of the potassium salts of N-phosphorylated thioureas of common formula R1-N(H)-C(S)-N(H)-P(O)(OiPr)2 (HA) with Ni II and PdII cations leads to [MA2] chelate complexes (M = NiII, R1 = p-MeOC6H4, p-BrC6H4, t-Bu, c-Hex; M = PdII, R = iPr). In both the NiII and PdII complexes, the metal center is found in a square-planar N2S2 environment formed by the C=S sulfur atoms and the P-N nitrogen atoms of two deprotonated ligands A -. The PdII atoms in [PdB2] complexes with deprotonated thioureas of common formula R2-C(S)-N(H)-P(O)(OiPr) 2 (HB) (R2 = Et2N, morpholine-N-yl) are coordinated in a square-planar fashion by the C=S sulfur atoms and the P=O oxygen atoms of two anionic ligands. Molecular structures of four complexes [M(A-N,S)2] (M = NiII, R1 = p-MeOC 6H4, p-BrC6H4, t-Bu; M = Pd II, R1 = iPr) and the palladium(II) 1,5-O,S-chelate of formula [Pd(B-O,S)2] (R2 = morpholine-N-yl) were elucidated by X-ray diffraction. © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.

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.

The catalytic activity of copper(I) complexes with N-thioacylamidothiophosphate ligands towards addition reaction of tetrachloromethane to alkenes was investigated. The influence of nucleophilic co-catalysts (alcohols, N-heterocycles, etc.) on catalytic activity of metal complexes was determined. © 2006 Elsevier B.V. All rights reserved.

The reaction of bis-thiourea o-C6H4[NHC(S)NHP(S)(Oi-Pr)2]2 (1) with iodine, KOH and ClCH2C(O)OCH3 leads to O,O′-diisopropyl-1,3-dihydro-2H-benzimidazol-2-ylideneamidothiophosphate (2) formation. The complex of the potassium salt of compound 2 with 18-crown-6, having the composition [K(18-crown-6)L], has been synthesized. Bis-thiourea [CH2NHC(S)NHP(S)(Oi-Pr)2]2 (6) forms a stable potassium salt, which oxidation by iodine leads to a product of heterocyclization, O,O′-diisopropyl-(1-{[(diisopropoxyphosphorothio)amino]carbonothioyl}imidazolidine-2-ylidene)amidothiophosphate (8), in which one of the thiourea fragments is kept. © 2006 Elsevier Ltd. All rights reserved.

Copper(II) bis-complexes with N-phosphoryl thioureas, RN′HC(S)NP(O) (OPri)2- {R = phenyl (I), cyclohexyl (II)}, have been obtained and investigated in liquid and frozen toluene solutions. Equilibria between trans-S,N and cis-S,N-isomers have been revealed and described by EPR method. In contrast to more usual S,O-forms, trans-S,N-isomers demonstrate large superhyperfine splitting from N and P atoms simultaneously. From EPR spectra anisotropic hyperfine, superhyperfine, and g-tensor parameters obtained and the symmetry of the metal ion surrounding analyzed. Rhombic anisotropy of copper(II) hyperfine and axial symmetry of N and P superhyperfine splitting resolved. Structural, hydrodynamic, and magnetic characteristics of the complexes established experimentally were supported by DFT calculations. According to EPR and DFT studies, tetrahedral distortion is higher in cis-S,N than in trans-S,N forms for steric reasons and slightly higher in I(S,N-trans) isomer than in II(S,N-trans) one due to the electron-donating effect of cyclohexyl substituent. The domination of S,N- over S,O-coordination is explained by the effects of the crystal field stabilization and the formation of the intramolecular hydrogen bonds. © 2005 Elsevier B.V. All rights reserved.

Heteroligand copper(I) complexes of bi- or bis-bidentate acylamidophosphates PhC(S)NHP(S)(OPr-i)2, PhC(S)NHP(O)(OPr-i) 2, Et2NC(S)NHP(S)(OPr-i)2, PhNHC(S)NHP(S)(OPr- i)2, N-(4-aminobenzo-15-crown-5)-C(S)NHP(S)(OPr-i)2, N,N-(1,10-diaza-18-crown-6)-[C(S)NHP(S)(OPr-i)2]2, and triphenylphosphine were prepared and characterised. Copper is bound by two PPh3 and one SCNPX (X = O, S) fragment of chelating ligand in all cases. Triphenylphosphine molecules reversibly dissociate in solution. Details of the X-ray structures of (Ph3P)2Cu[PhC(S)NP(S)(OPr-i) 2] and (Ph3P)2Cu[Et2NC(S)NP(S)(OPr- i)2] are reported. © 2005 Elsevier B.V. All rights reserved.

Reaction of the potassium salts of N-thioacylamidophosphates RC(S)NHP(O)(OPri)2 (R = Ph, PhNH, p-MeOPhNH, p-BrPhNH, iPrNH, tBuNH, Et2N, c-C5H10N, c-OC4H8N, c-C5H11NH) with Co(II) cation in aqueous EtOH leads to the complexes of Co(L-O,S)2 type structure. Complexes Co(B)L2 were obtained by the reaction of chelate complexes CoL2 (R = Ph, PhNH) with 2,2′-bipyridine and 1,10-phenanthroline. Structures of the compounds obtained were investigated by EIMS, IR, UV-Vis spectroscopy and microanalysis. Complex Co[PhC(S)NP(S)(OPri)]2 was investigated by single crystal X-ray diffraction. © 2006 Elsevier Ltd. All rights reserved.

N-Acylamidophosphinates RC(X)NHP(Y)R′2 (NAAP) and their thioanalogues (X,Y=O, S; R = Alk, Ar, CCl3, Het, NR2 2, NR2R3; R' = Ar, OAlk, OAr, SAlk, NAlk2, NHAr) contain X, Y donor atoms and amide nitrogen, which are capable of taking in complexation with metal cations. An application of NAAP complexes in supramolecular chemistry has been investigated in the last decades. Developed synthetic methods allow us to obtain N-acylamidophosphinate ligands contained multiple chelating groups or a combination of several essentially various coordinating fragments in the molecule: chelating moiety C(X)NHP(Y) and a macrocycle. The latter ligands are capable of connecting ions simultaneously by the chelating sites, and by the "guest-host" mechanism using the macrocycle. The bibliography includes 104 references. © 2006 Bentham Science Publishers Ltd.

Reaction of the potassium salt of N-(diisopropoxyphosphoryl)thiobenzamide (iPrO)2P(O)NHC(S)C6H5 (HL) with ZnII and CdII cations in aqueous EtOH leads to three different complexes: [Zn(L-O,S)2] (1), [Cd2(L-O,S)4] (2) and [Cd(HL-O)2(L-O,S)2] (3). The structures of these compounds were investigated by single-crystal X-ray diffraction analysis, EI-MS and ES-MS, IR, 1H, 13C and 31P NMR spectroscopy and microanalysis. The zinc(II) atom in complex 1 is in a distorted tetrahedral ZnO2S2 environment formed by the C=S sulfur atoms and the P=O oxygen atoms of two deprotonated ligands. The cadmium(II) complex 2 is centrosymmetric and consists of dimeric species. Two [Cd(L-O,S)2] moieties are connected by two bridging [S-Cd-S] units through the sulfur atoms of the ligand C=S groups. Complex 2 has a distorted trigonal-bipyramidal Cd(Oax)2(Seq)3 core. Complex 3 has a tetragonal-bipyramidal environment, Cd(Oax)2(O eq)2(Seq)2, and two neutral ligand molecules are coordinated in the axial positions through the oxygen atoms of the P=O groups. The base of the bipyramid is formed by two anionic ligands in a typical 1,5-O,S coordination mode. The ligands are in a trans configuration. © Wiley-VCH Verlag GmbH & Co. KGaA, 2006.

Thiourea, PhNHC(S)NHP(O)(OPri)2 (LH) chelates of CoII, NiII, and PdII ions have been obtained and investigated by single-crystal X-ray diffraction, UV, IR, NMR spectroscopy, and EI mass-spectrometry. The unusual 1,3-N,S-coordination via sulfur and NP(O) nitrogen atoms has been found in the trans-square-planar NiL2 and PdL2 complexes, whereas the 1,5-O,S-coordination is realized in the tetrahedral CoL2 complex. DFT calculations have revealed significant stabilization of the 1,3-N,S-structures due to stronger crystal field and the NH-O{double bond, long}P hydrogen bonds. © 2006 Elsevier B.V. All rights reserved.

The reaction of potassium salts of N-thiocarbamoylamidophosphates RC(S)NHP(O)(OPr-i)2X [X = PhNH, p-MeOPhNH, p-BrPhNH, i-PrNH, t-BuNH, Et2N, C5H10N, OC4H8N, C 6H11NH] with Zn(II) cation gives complexes of the composition Zn(L-O,S)2. The Cd(II) complexes could not be isolated under analogous conditions because of their hydrolytic lability. The reaction of thioureas (X = PhNH, p-MeOPhNH) with Cd(II) acetate in DMF provides stable solvato complexes of the composition Cd(DMF)2L2. The structure of the resulting compounds was studied by means of IR, 1H, and 31P NMR spectroscopy and EI and ESI mass spectrometry. © 2005 Pleiades Publishing Inc.

The acid-base and coordination properties of N-thiophosphorylated thioureas with respect to Ni2+, Co2+, Cd2+, Zn 2+, and Pd2+ ions were studied by UV spectrophotometry in 96% isopropanol. The stability constants pK and the maximum accumulated fractions of complex species in solution were calculated.

The title complexes CoL2 and CoL2·2HL were synthesised and characterised using IR spectroscopy, mass spectrometry and single-crystal X-ray diffraction analysis.