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A family of three- and four-coordinated silver(I) complexes of formulas [Ag(PPh3)2L], [Ag(PPh3)L], and [AgL]n with N-thiophosphorylated thiourea and thioamide ligands of general formula RC(S)NHP(S)(OPri)2 [R = Ph, PhNH, iPrNH, tBuNH, NH2] have been studied by solid-state 109Ag and 31P CPMAS NMR spectroscopy. 109Ag NMR spectra have provided valuable structural information about Ag coordination, which is in good accordance with the available crystal structure data. The data presented in this work represent a significant addition to the available 109Ag chemical shifts and chemical shifts anisotropies. The silver chemical shift ranges for different P,S-environments and coordination state were discussed in detail. The 1J(31P–107/109Ag) and 2J(31P–31P) values were determined and analyzed. © 2022 John Wiley & Sons Ltd.

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.

With the intention of building hollow tubular structures by self-assembly, we have designed and successfully synthesized a series of calix[8]arene derivatives. Their phenolic units were functionalized in p-position by various groups which are able to interact via hydrogen bonding or π-π stacking. Ethynyl, amide, urea, or imide links were chosen for the covalent attachment of these functional groups, to ensure the adjustment of an optimal distance for their interaction. Two different kinds of nanostructures selfassembled on a highly oriented pyrolytic graphite (HOPG) surface were found by scanning force microscopy: parallel aligned nanorods in which the calixarene molecules are adsorbed edge-on on the graphite, providing evidence that these calix[8]arene derivatives stack in a tubular fashion, and micrometer long fiber bundles most probably composed of many nanorods. © 2005 American Chemical Society.

N-Thiophosphorylated thioureas, of general formula [(i-PrO)2 P(S)NHC(S)]2Z (Z = α,ω-diamino(oxy)alkyl or 1,10-diaza-18-crown-6), in the form of potassium salts, react with a number of soft ions (Cd2+, Zn2+, Co2+, Ni2+, Pd2+) to form novel dimeric complexes. The cadmium (Z = HN(CH2)2NH), palladium (Z = HN(CH2)2O(CH2)2NH), and cobalt (Z = 1,10-diaza-18-crown-6) complexes were analyzed by x-ray crystallography. In the former complex, crown cavities remain free. This fact will allow us to obtain "guest-host" complexes with alkali metal cations.

With the intention of building hollow tubular structures by self-assembly, we have designed and successfully synthesized a series of calix[8]arene derivatives. Their phenolic units were functionalized in p-position by various groups which are able to interact via hydrogen bonding or π-π stacking. Ethynyl, amide, urea, or imide links were chosen for the covalent attachment of these functional groups, to ensure the adjustment of an optimal distance for their interaction. Two different kinds of nanostructures selfassembled on a highly oriented pyrolytic graphite (HOPG) surface were found by scanning force microscopy: parallel aligned nanorods in which the calixarene molecules are adsorbed edge-on on the graphite, providing evidence that these calix[8]arene derivatives stack in a tubular fashion, and micrometer long fiber bundles most probably composed of many nanorods. © 2005 American Chemical Society.

N-Thiophosphorylated thioureas, of general formula [(i-PrO)2 P(S)NHC(S)]2Z (Z = α,ω-diamino(oxy)alkyl or 1,10-diaza-18-crown-6), in the form of potassium salts, react with a number of soft ions (Cd2+, Zn2+, Co2+, Ni2+, Pd2+) to form novel dimeric complexes. The cadmium (Z = HN(CH2)2NH), palladium (Z = HN(CH2)2O(CH2)2NH), and cobalt (Z = 1,10-diaza-18-crown-6) complexes were analyzed by x-ray crystallography. In the former complex, crown cavities remain free. This fact will allow us to obtain "guest-host" complexes with alkali metal cations.

The complexes (PriO)2P(S)NHC(S)R (R = NEt 2, NHPh), [(PriO)2P(S)NHC(S)] 2-1,10-diaza-18-crown-6 have been obtained by the metathesis reaction of potassium salts of corresponding thiophosphorylated thioureas with (PPh3)2CuNO3; the crystal structure of (Ph 3P)2Cu[Et2NC(S)NP(S)(OPri) 2] has been confirmed by X-ray crystallography.

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.

The complexes (PriO)2P(S)NHC(S)R (R = NEt 2, NHPh), [(PriO)2P(S)NHC(S)] 2-1,10-diaza-18-crown-6 have been obtained by the metathesis reaction of potassium salts of corresponding thiophosphorylated thioureas with (PPh3)2CuNO3; the crystal structure of (Ph 3P)2Cu[Et2NC(S)NP(S)(OPri) 2] has been confirmed by X-ray crystallography.

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.

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.

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 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.

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.

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.

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.

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.

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.

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.

Gold and silver complexes with the N-[bis(isopropoxy)-thiophosphoryl]thiobenzamide (HL1) and N-[bis(isopropoxy)-thiophosphoryl]-N′-phenylthiourea (HL2) ligands are reported, The compounds [M(HL)(PPh3)]TfO, [Ag(HL)(TfO)] and [Ag(HL)(PPh3)2]TfO were obtained by the reaction of both ligands with the corresponding trifluoromethanesulfonate salts. The (acetylacetonato)gold and -silver materials [M(acac)(PPh3)] or [Au(acac)(C6F5)2] cause deprotonation of the ligands and afford [ML(PPh3)] or [AuL(C6F 5)2], whereas the reaction of [Au(TfO)(PPh3)] with HL1 in a 2:1 molar ratio in KOH/MeOH affords [Au 2(L1)(PPh3)2]TfO, The first homoleptic anionic metal compounds [AuIL2]- are also reported. © Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Crystals of the title calixarene containing CCl4 as solvent have already been investigated [Baudry, Felix, Bavoux, Perrin, Vocanson, Dumazet-Bonnamour & Lamartine (2003). New J. Chem. pp. 1540-1543]. We present here a new pseudopolymorph of this compound, C64H 56Br8O8·2C4H8O, containing tetrahydrofuran as solvent and crystallizing in a different space group. However, the molecular conformation of both molecules is very similar. Further similarities of both structures are that the calixarene molecules are located on a centre of inversion and that the solvent molecules occupy similar positions with respect to the calixarene molecules. © 2003 International Union of Crystallography Printed in Great Britain - all rights reserved.

(Equation presented) Octamethoxy calix[8]arenes substituted in the para position by amide, urea, and imide functions were synthesized from the octamethyl ether of tert-butylcalix[8]arene by ipso nitration, reduction, and acylation. Scanning force microscopy of spin coated samples on graphite suggests that these derivatives self-organize into tubular nanorods via hydrogen bonds between p-amide functions. A single-crystal X-ray structure reveals a centrosymmetric conformation for the octanitro derivative.