Novel bicyclic hexanuclear copper(I) aggregate: Structure and solid state P 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.     

On some generalization of the DEA models

Inadequate results may arise in some instances of DEA model applications. For example, a data envelopment analysis (DEA) model may show ‘a notoriously inefficient unit’ as an efficient one. In addition, too many efficient units may appear in some DEA models. An elegant and subtle approach was proposed to deal with these problems, which is based on incorporating domination cones in DEA models. Yu, Wei and Brockett suggested the generalized DEA (GDEA) model that unifies and extends most of the well-known DEA models based on using domination cones. In this paper, we propose a model that is more general than the GDEA model, on the one hand, as it covers situations that the GDEA model cannot describe. On the other hand, our model enables one to construct step-by-step any model from the family of the GDEA models by incorporating artificial units and rays in the space of inputs and outputs in the Banker, Charnes, Cooper (BCC) model, which makes the process of model construction visible and more understandable. Moreover, we show that any GDEA model can be approximated by some BCC model.     

Bordism groups of special generic mappings

The Pontrjagin-Thom construction expresses a relation between the oriented bordism groups of framed immersions , and the stable homotopy groups of spheres. We apply the Pontrjagin-Thom construction to the oriented bordism groups of mappings n$">, with mildest singularities. Recently, O. Saeki showed that for , the group is isomorphic to the group of smooth structures on the sphere of dimension . Generalizing, we prove that is isomorphic to the -th stable homotopy group , , where is the group of oriented auto-diffeomorphisms of the sphere and is the group of rotations of .

     

Competition between n,π- and n,σ-orbital interactions in chlorinated ethers R-O-chcir 1

Using the AM-1 method, we have studied CH₂=CH-O-CHClR¹ molecules (R¹=H, Me). We have shown that the sc conformation with respect to the bond is preferred. We have systematized the¹³Cl NQR data on the degree of manifestation of the generalized anomeric effect in R-OCHClR¹ [R=Me, Ph, Vyn, R²C(=O)] molecules. We have established that enhancement of n, conjugation in the R-O fragment leads to weakening of the n, interaction in the O-C-Cl triad.Deceased.     

Membrane extraction of alkaline earth metal by phosphorylated azapodands

ABSTRACT

Membrane transport properties of the new lipophilic phosphorylated azapodands toward Сa(II), Ва (II), Mg(II), and Sr(II) were studied. The investigation of the processes of passive membrane ion transport showed the high values of the transfer flow of the alkaline earth metals’ ions with all carriers. It was found that N,N’-bis(di-p-tolylphosphorylmethyl)-1,8-diamino-3,6-dioxaoctane (I) is the most effective carrier among all compounds studied.     

On double polarization asymmetries in the elastic electron-proton scattering

Double polarization asymmetry D_p^(M) for the process of elastic electroweak scattering of the longitudinally polarized electrons by polarized proton target is considered with account of anapole G_1p and electric dipole moment (EDM) G_2p proton form factors. This asymmetry is only due to T-parity violating form factor G_2p, but does not directly depend on it, and having a significant value, allows to confirm the existence of the EDM of the proton.     

Complexes of N‐Thiophosphorylthiourea tBuNHC(S)NHP(S)(OiPr)2 with Zinc(II), Cadmium(II), Nickel(II), and Cobalt(II) Cations

Reaction of the potassium salt of N‐thiophosphorylthiourea tBuNHC(S)NHP(S)(OiPr)₂ ( HL ) with Zn^II, Cd^II, Ni^II and Co^II 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.     

Complexes of N-thiophosphorylthiourea (EtO)2P(O)CH2C6H4-4-[NHC(S)NHP(S)(OiPr)2] with Zn(II), Cd(II), Co(II) and Cu(PPh3)(I)

Reaction of O,O’-diisopropylthiophosphoric acid isothiocyanate (iPrO)₂P(S)NCS with diethyl 4-aminobenzylphosphonate (EtO)₂P(O)CH₂C₆H₄-4-NH₂ leads to the new N-thiophosphorylated thiourea (EtO)₂P(O)CH₂C₆H₄-4-[NHC(S)NHP(S)(OiPr)₂] (HL). Reaction of the potassium salt of HL with Zn(II), Cd(II) and Co(II) in aqueous EtOH leads to complexes of formula M(L-S,S’)₂ (ML₂). Heteroligand copper(I) complex of HL and triphenylphosphine was prepared by the reaction of the potassium salt KL and Cu(PPh₃)₃I. Copper in complex Cu(PPh₃)L is bound by one PPh₃ and one SCNPS fragment of the chelating ligand. Compounds obtained were investigated by IR, UV–Vis, ¹H and ³¹P{¹H} NMR spectroscopy, and microanalysis. The structures of HL and Cu(PPh₃)L were investigated by single crystal X-ray diffraction analysis.