First paramagnetic PdII complex with a PdN4S 2 coordination core

Reaction of the potassium salt of N-thiophosphorylated thiourea 2-PyNHC(S)NHP(S)(OiPr)2 (HL) with PdCl2 in aqueous MeOH leads to the formation of two mononuclear homoleptic complexes [Pd{2-PyNHC(S)NP(S)(OiPr)2-1,5-S,S′}2] ([Pd(L-1,5-S,S′)2]) and [Pd{2-PyNHC(S)NP(S)(OiPr) 2-1,5,7-N,N′,S}2] ([Pd(L-1,5,7-N,N′,S) 2]), while the mechanically induced solid-state reaction of KL and PdCl2 leads to the exclusive formation of [Pd(L-1,5,7-N,N′,S) 2]. The dithiocoordinated desmotrope is square-planar and diamagnetic, while the second desmotrope is unprecedentedly octahedrally configured and paramagnetic. © The Royal Society of Chemistry 2013

Heteroleptic Cu(I) and Ag(I) complexes of N-thiophosphorylated tris-thioureas and triphenylphosphane

The reaction between tris(2-aminoethyl)amine or diethylenetriamine and O,O′-diisopropyl-isothiocyantothiophosphate (iPrO) 2P(S)NCS gives the tris-functional thioureas N(CH 2CH 2NHC(S)NHP(S) (OiPr) 2) 3 (H 3L I) and N(C(S)NHP(S)(OiPr) 2)(CH 2CH 2NHC(S)NHP(S)(OiPr) 2) 2 (H 3L II) with three C(S)NHP(S)(OiPr) 2 groups. The reaction of the potassium salts K 3L I,II with a mixture of CuI or AgNO 3 and PPh 3 in aqueous EtOH/CH 2Cl 2 leads to the [M 3(PPh 3) 6L I,II] complexes. According to the IR, 1H and 31P{ 1H} NMR data, the deprotonated thioureas L I,II are coordinated through the sulfur atoms of the thiocarbonyl and thiophosphoryl groups in [M 3(PPh 3) 6L I,II], both in the solid state and in solution. The complexes [Cu 3(PPh 3) 6L I,II] and [Ag 3(PPh 3) 6L I,II] show emissions in the solid state at about 465 and 490 nm, respectively. © 2011 Elsevier Ltd. All rights reserved

Influence of the coordination mode in [Ni{RC(S)NP(S)(OiPr)2)2] for the formation of nickel-containing nanoparticles

The complex [Ni{2-PyNHC(S)NP(S)(OiPr) 2-1,5,7-N,N′,S} 2] ([NiL I 2]) dissolved in tri-n-octylphosphine (TOP) is decomposed in hot hexadecylamine (HDA) to give TOP-capped Ni nanoparticles. The same procedure using [Ni{2-MeC 6H 4NHC(S)NP(S)(OiPr) 2} 2-1,3-N,S] ([NiL II 2]) and [Ni{PhC(S)NP(S)(OiPr) 2-1,5-S, S′} 2] ([NiL III 2]) leads to the formation of NiS nanoparticles with the rhombohedral and hexagonal structures, respectively. NiH x nanoparticles were also produced from a mixture of [NiL I 2] and N 2H 4. The obtained Ni nanoparticles can be used for the catalytic addition of Ph 2S 2 to 1-, 2- and 3-hexynes. © The Royal Society of Chemistry 2012

C-H⋯Br-C: Vs. C-Br⋯Br-C vs. C-Br⋯N bonding in molecular self-assembly of pyridine-containing dyes

We have studied a series of closely related N-(5-bromosalicylidene)-x-aminopyridine compounds (x = 2, 1; 3, 2; 4, 3), obtained by condensation of 5-bromosalicylaldehyde with the corresponding aminopyridine. 1H NMR spectroscopy in solution revealed a single structure, at least in CDCl3. According to single crystal X-ray diffraction it was established that the crystal structures of 1-3 each are stabilized by a linear intramolecular hydrogen bond of the O-H⋯N type, formed between the hydroxyl hydrogen atom of the phenolic ring and the imine nitrogen atom. The dihalogen C-Br⋯Br-C and halogen C-Br⋯N(Py) interactions play a crucial role for the formation of supramolecular architectures in the structures of 2 and 3, respectively. The overall geometry of each molecule in the structures of 1 and 2 was found to be almost planar, while a significantly twisted structure was found for 3. Hirshfeld surface analysis showed that the structures of all compounds are mainly characterized by H⋯X contacts as well as by a remarkable contribution from C⋯C and C⋯N contacts which is clearly observed for 1 and 2. Diffuse reflectance spectra of 1-3 each exhibit a mixture of enol, cis-keto and trans-keto forms. A major contribution of the trans-keto form is found for 1 whereas a moderate fraction is detected for 2, and only traces of the trans-keto form were observed for 3. Contrary to expectations based on dihedral angle Φ considerations, 1 exhibits negative photochromism, although it was expected to be only thermochromic. Both 2 and 3 are not photochromic, whereas 3 was expected to be photochromic (Φ > 25°). Highly favoured C⋯C, C⋯N and O⋯Br intermolecular contacts as well as the absence of Br⋯Br dihalogen interactions in the structure of 1, are presumably mainly responsible for the photochromic behaviour. Furthermore, significantly impoverished H⋯C and H⋯N contacts further support the observed negative photochromism of 1. © 2016 The Royal Society of Chemistry

Complexation properties of the crown ether-containing N-thiophosphorylated thiourea towards Ni II

Reaction of the deprotonated N-thiophosphorylated thiourea (4′-benzo-15-crown-5)NHC(S)NHP(S)(OiPr) 2 (HL) with NiCl 2 in aqueous EtOH leads to dark green [Ni(L-1,5-S,S′) 2]·2H 2O crystals that were isolated by recrystallization from a mixture of CH 2Cl 2 and n-hexane. © 2012 The Royal Society of Chemistry

Decomposition of the mixed-ligand silver(I) complex [Ag(PPh3)2{Et2NC(S)NP(S)(OiPr)2}] with the formation of [Ag(PPh3){Et2NC(S)NP(S)(OiPr) 2}], [Ag(PPh3)3NCS]·(CH3)2C=O and Et2NP(S)(OiPr)2

Reaction of the potassium salt of the N-thiophosphorylated thiourea Et 2NC(S)NHP(S)(OiPr) 2 (HL) with a mixture of AgNO 3 and PPh 3 in aqueous EtOH/CH 2Cl 2 leads to the mixed-ligand silver(I) complex [Ag(PPh 3) 2{Et 2NC(S)NP(S)(OiPr) 2}] ([Ag(PPh 3) 2L]). Recrystallization of [Ag(PPh 3) 2L] from an acetone/n-hexane mixture leads to the decomposition of the starting complex with the formation of [Ag(PPh 3){Et 2NC(S)NP(S)(OiPr) 2}] ([Ag(PPh 3)L]), [Ag(PPh 3) 3NCS]·(CH 3) 2C=O and Et 2NP(S)(OiPr) 2. The structures of [Ag(PPh 3) 2L], [Ag(PPh 3)L], [Ag(PPh 3) 3NCS]·(CH 3) 2C=O and Et 2NP(S)(OiPr) 2 were all investigated by IR, 31P{ 1H} and 1H NMR spectroscopy, and their compositions were established by elemental analysis. The crystal structure of the complex [Ag(PPh 3) 3NCS]·(CH 3) 2C=O obtained from single crystal X-ray diffraction is presented. © 2011 Elsevier B.V. All rights reserved

Organic matrix-induced formation of a discrete cyclic [Cl2(H2O)2]2– hybrid cluster

Reaction of 6-NH2-Py-2-NHC(S)NHP(S)(OiPr)2 with DMFA·2HCl leads to the co-crystallization product of 2,6-di(4H-1,2,4-triazol-4-yl)pyridine and 2,6-diaminopyridinium chloride monohydrate (1) and N-(diisopropoxythiophosphoryl)-N′-(6-(4H-1,2,4-triazol-4-yl))pyridin-2-ylthiocarbamide (2).</p

Detailed studies of the interaction of 3-chloroaniline with O,O′-diphenylphosphorylisothiocyanate

The reaction of neat 3-chloroaniline with neat S[double bond, length as m-dash]C[double bond, length as m-dash]N–P(O)(OPh)2 leads to a new N-phosphorylated thiourea, 3-ClC6H4NHC(S)NHP(O)(OPh)2 (1). The same reaction in non-dried CH2Cl2 or C6H6 leads to the salt-like compounds [3-ClC6H4NH3]+[NCS]− (2) and [3-ClC6H4NH3]+[P(O)2(OPh)2]−·0.5C6H6 (3·0.5C6H6), respectively, while using non-dried acetone yields 1-(3-chlorophenyl)-4,4,6-trimethyl-3,4-dihydropyrimidine-2(1H)-thione (4). Dissolution of 1 in non-dried CH2Cl2, C6H6 or Me2C[double bond, length as m-dash]O leads to the direct formation of 2, 3·0.5C6H6 and 4, respectively. It was established that thione 4 is most likely formed through the thiourea 1-assisted aldol condensation of acetone leading to mesityl oxide. In turn the latter ketone interacts with 1 followed by its hydrolysis leading to 4. Compounds 1–4 have been characterized by NMR spectroscopy and elemental analysis and their molecular structures were elucidated by X-ray diffraction. Hirshfeld surface analysis showed that the structures of both 1 and 4 are mainly characterized by H⋯H, H⋯C, H⋯Cl and H⋯S contacts as well as by H⋯O in the structure of 1. The enrichment ratio, derived as the decomposition of the crystal contact surface between pairs of interacting chemical species, for 1 was found, as expected for the polar contacts, which are generally hydrogen bonds, to be significantly larger than unity for the contacts of the type H⋯O and H⋯S. A much larger than unity value was found for the enrichment ratio of the C⋯C contacts in the structure of 1, which is due to extensive π⋯π stacking in the crystal packing. The enrichment ratio for 4 was found to be larger than unity for the contacts of the type H⋯C and, but with a lesser degree, H⋯Cl and H⋯S

Homoleptic polynuclear CuI and AgI complexes of N-thiophosphorylated thioureas o-RO(O)CC6H4NHC(S)NHP(S)(OiPr)2 (R = Me, Et)

Reaction of the deprotonated N-thiophosphorylated thioureas o-RO(O)CC 6H 4NHC(S)NHP(S)(OiPr) 2 (R = Me, HL I; Et, HL II) with CuI and AgNO 3 leads to the homoleptic polynuclear complexes [Cu 3L I,II 3], [Ag 4L I 4] and [Ag 5L II 5]. The crystal structures of the former three complexes were determined by single-crystal X-ray diffraction. The nuclearity of the latter complex was established by the reaction with 1,10-phenanthroline (phen) with the exclusive formation of the heteroleptic mononuclear complex [Ag(phen)L II]. The same mixed-ligand complex was also obtained by the reaction of KL II with a mixture of CuI and phen. The complex [Ag 5L II 5] is the first example of a homoleptic polynuclear Ag I complex with RC(S)NHP(S)R′ 2 exhibiting a pentanuclear structure. © 2012 The Royal Society of Chemistry

N-(Diisopropylthiophosphoryl)-N′-(R)-thioureas: Synthesis, characterization, crystal structures and competitive bulk liquid membrane transport of some metal ions

Ten N-thiophosphorylated thioureas of the common formula RC(S)NHP(S)(OiPr) 2 [R = iPrNH (1), EtNH (2), Et 2N (3), 2,5-Me 2C 6H 3NH (4), 4-Me 2NC 6H 4NH (5), 2-MeO(O)CC 6H 4NH (6), 2-PyNH (7), 2-PyCH 2NH (8), 3-PyCH 2NH (9), cyclo-C 2H 2N 3NH (10)] have been synthesized and characterized by IR, NMR spectroscopy and elemental analysis. Molecular structures of 1 and 4-8 were elucidated by X-ray diffraction revealing linear, bi- or trifurcated intramolecular hydrogen bonds. Additionally, their crystal structures are stabillized by two intermolecular hydrogen bonds, which in turn lead to a centrosymmetric dimer formation. The hydrogen bonded dimers of 5-8 are packed to polymeric chains through the π⋯π stacking interactions between aryl or pyridyl rings. Competitive transport experiments involving metal ions from an aqueous source phase through a chloroform membrane into an aqueous receiving phase have been carried out using 2-6 and 8-10 as the ionophore present in the organic phase. The source phase contained equimolar concentrations of Co II, Ni II, Cu II, Zn II, Ag I, Cd II and Pb II with the source and receiving phases being buffered at pH = 5.5 and 1.0, respectively. The obtained data were compared with the transport and extraction properties of 1 and 7, which were described recently. © The Royal Society of Chemistry 2012