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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 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.

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 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.

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.

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 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.

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 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.