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Reaction of RNHC(S)PPh2NPPh2C(S)NR (HRSNS; R = Me, Et) with Ml (M = Cu, Ag, Au) salts afforded zwitterionic complexes of the general formula [M(RSNS)] (M = Cu, Ag, Au). The ligand was found in the solid state in S,S-k² and S,N,S-k³ coordination fashions. [Cu(RSNS)] and [Ag(RSNS)] can be used as metalloligand building blocks for the assembly of pentanuclear multizwitterionic Cu5, Cu3Ag2 and Ag5 core clusters of the general formula [M′2{M(RSNS)}3]2+ (M = Cu, M′ = Cu, Ag; M = M′ = Ag) upon reaction with suitable M′ salts. The crystal structures of the most significant compounds are reported herein. Compound [Ag2{Ag(RSNS)}2(OTf)2] was also isolated and structurally characterized, representing a model for the intermediate species of the aforementioned assembly. [ABSTRACT FROM AUTHOR]

New Group 4 metal t-butyldimethylsilylcyclopentadienyl complexes [MCpCp′Cl2] (Cp=η5-C5H5; Cp′=η5-C5H4SiMe2tBu; M=Ti 4, Zr 5, Hf 6) were prepared by reaction of 1 equiv. of the lithium (2) and thallium (3) salts of t-butyldimethylsilylcyclopentadiene 1 with the monocyclopentadienyl complexes [MCpCl3·DME] (M=Zr, Hf) and [TiCpCl3], respectively. A similar reaction using ZrCl4(THF)2 and HfCl4 with 2 equiv. of the lithium salt 2 gave the symmetric [MCp′2Cl2] ( M=Zr 7, Hf 8) metallocenes. Alkylation of these compounds with 2 equiv. of MgRCl (R=Me, CH2Ph) and Li(CH2CMe2Ph) afforded the dialkyl complexes [MCpCp′R2] (R=Me, M=Zr 9, Hf 10; R=CH2Ph, M=Ti 11, Zr 12, Hf 13), [ZrCp′2(CH2Ph)2] 14 and [ZrCpCp′(CH2CMe2Ph)2] 17. A Similar reaction of 5 with 1 equiv. of Mg(CH2Ph)Cl gave the monobenzyl compound [ZrCpCp′Cl(CH2Ph)] (15). Hydrolysis of 15 with a stoichiometric amount of water afforded the dinuclear μ-oxo compound [(ZrCpCp′Cl)2(μ-O)] (16). All of the new complexes reported were characterized by elemental analysis and 1H and 13C NMR spectroscopy and the molecular structures of 4 and 16 were determined by X-ray diffraction methods. Ethylene polymerization activities were measured for compounds 4–7. [Copyright &y& Elsevier]

Preparations of copper(II) and palladium(II) complexes of 4-amino-5-methylthio-3-(2-pyridyl)-1,2,4-triazole (L1) and the copper(II) complex of 1,4-dihydro-4-amino-3-(2-pyridyl)-5-thioxo-1,2,4-triazole (HL) are described. These complexes have been characterized by means of spectroscopy and microanalysis. Molecular structures of HL (1), [CuCl2(H2L)]Cl·2H2O (2a), cis-[CuCl2(L1)] (3), and cis-[PdCl2(L1)] (4) have been determined by single-crystal X-ray diffraction. The HL ligand acts as a N,S bidentate through the thioxo moiety and the exo-amino group whilst the ligand L1 forms N,N coordination complexes through the pyridine and triazole nitrogen atoms. Speciation in solution of the systems Cu/HL and Cu/L1 have been determined by means of potentiometry and spectrophotometry as well as for the Cu/L1/A (HA=glycine) system in order to determine species present at physiological pH. Antiproliferative activity of these complexes and their ligands was evaluated, using the AlamarBlue™ Assay, on normal human fibroblasts (HF) and human fibrosarcoma tumor (HT1080) cells. The copper compounds cis-[CuCl2(H2L)]Cl and cis-[CuCl2(L1)] exerted significant antiproliferative activity of both normal and neoplastic cells; although dose–response experiments revealed that the HT1080 cell line was more sensitive to the tested drugs than normal fibroblasts. [ABSTRACT FROM AUTHOR]

In Italy, the consumption of pork meat is increasing, despite consumers' attitudes being addressed toward a greater sensitivity about animal welfare and its link with safe food. Considering the relatively high animal welfare standards and the divergence in public interest in farm animal welfare and ethical issues, the objective of this study-in continuation of our previous paper relating to consumer behavior and preferences in welfare-friendly pork breeding-was to investigate habits of pork consumers regarding pig welfare, principally evaluating their willingness to pay (WTP) a higher price for pork obtained using raising techniques with an approach based on animal welfare. An ad hoc questionnaire-based survey was submitted to consumers (n = 404) in Messina province, Italy. Results suggest that 47% of consumers were willing to pay an additional price for pork from farms that apply specific animal welfare standards. Positive correlations were between WTP and farming techniques ( p = 0.001), organic farming methods ( p = 0.001), and farms in which animal welfare is taken care of and guaranteed ( p < 0.001). These findings suggest that consumers intend to pay a higher price for pork, like other animal products obtained using animal-friendly raising techniques. The sensitivity to the animal welfare of a single human being may influence consumers' attitudes toward pork consumption.

This study investigates consumer behavior and interest in "welfare-friendly" forms of pork production, considering the growing presence of animal welfare-focused breeding practices. The aim is to outline the typical profile of pork consumers and identify the key attributes influencing their purchasing decisions. A survey was conducted on a sample of 286 individuals after excluding those who only consumed beef and/or poultry or identified as vegetarians/vegans. Regression coefficients (b), 95% Confidence Intervals (95% C.I.), and p -values were reported for univariate and multivariate models. Statistical significance was determined at p < 0.05 (indicated in bold). The findings indicate that younger participants show greater sensitivity towards consuming meat raised using welfare-friendly methods, raising considerations about the age composition of the sample. The research's originality lies in evaluating consumer interest in pork raised with animal welfare-respecting techniques. The use of appropriate statistical tools, such as multivariate and multilayer models, allows effective solutions for multidimensional hypothesis testing problems in non-parametric permutation inference.

The reactivity of platinum(II) complexes of the type [PtCl(O,O-acac)(L)] (1) and [Pt(O,O-acac)(gamma-acac)(L)] (2) (L = DMSO, a; DMS, b), with a range of hard and soft nucleophiles such as dimethylsulfide (DMS, b), triphenylphosphine, (PPh3, c), ethylene (eta2-C2H4, d), carbon monoxide (CO, e), pyridine (py, f), and guanosine (Guo, g) has been investigated. Interestingly, the complexes 1a and 1b undergo selective substitution of the chloro or sulfur ligand depending on the hard/soft character of the incoming nucleophile. The soft incoming ligand replaces the softer one and the hard ligand replaces the harder one, giving [PtCl(O,O'-acac)(L)] complexes (1b, 1c, 1d and 1e in the reaction of 1a with L = DMS, PPh3, eta2-C2H4, CO, respectively), and [Pt(O,O'-acac)(DMSO)(L')] (3f, 3g) and [Pt(O,O'-acac)(DMS)(L')] (4f, 4g) species in the reaction of 1a and 1b with L' = py and guo, respectively. In the cases of 2a and 2b complexes, where the pi-bonded acac (gamma-acac) replaces the chloro ligand, only in the presence of an incoming soft nucleophile substituting the soft sulfur ligand the reaction occurs. Equilibrium constants for the substitution reactions were measured by 1H NMR spectroscopy. Variable temperature 1H NMR spectroscopy studies, performed for the reaction of 1a and 2a complexes with DMS, revealed that the selective substitution of DMSO with DMS takes place in both cases, according to a second-order kinetic law. The calculated values of DeltaH++ and DeltaS++ are consistent with an associative mechanism. NMR spectroscopic characterization (1H, 13C, 195Pt, 31P) for the complexes and crystal structures of isolated complexes ([PtCl(O,O'-acac)(L)] (1) and [Pt(O,O'-acac)(gamma-acac)(L)] (2), L = DMSO, 1a and 2a; L = DMS, 1b and 2b; L = PPh3, 1c and 2c) are herein reported and discussed.

The heteroscorpionate N, N', S, S' donor ligands 4-methoxy-3,5-dimethyl-2-(3-(methylthio)-1-(3-(2-(methylthio)phenyl)-1H-pyrazol-1-yl)propyl)pyridine (L(a)) and 4-methoxy-3,5-dimethyl-2-(2-(methylthio)-1-(3-(2-(methylthio)phenyl)-1H-pyrazol-1-yl)ethyl)pyridine (L(b)) were prepared. The Cu(I) complexes [Cu(L(a))]2(BF4)2 (a2(BF4)2) and [Cu(L(b))]2(BF4)2 (b2(BF4)2) were synthesized and characterized by X-ray crystallography. Both compounds exhibit a dinuclear structure, presenting each Cu(I) center in a distorted N, N', S, S' tetrahedral environment. On the basis of nuclear magnetic resonance (NMR) and ESI-mass data, the presence of a mononuclear complex in equilibrium with the dimer was hypothesized for both complexes. The dimerization constants of the processes, 2a(+) = a2(2+) and 2b(+) = b2(2+) , were obtained by (1)H NMR dilution experiments (fast-exchange regime) in CD 3CN: log K(a2(2+)) = 3.55(6) and log K(b2(2+)) = 3.23(5) at 300 K. Thermodynamic parameters were determined by a van't Hoff analysis (280-310 K temperature range): DeltaH(0)(a2(2+)) = -12(1) kJ mol (-1), DeltaH(0)(b2(2+)) = -10(1) kJ mol(-1), DeltaS(0)(a2(2+)) = +27(4) kJ mol (-1), and DeltaS(0)(b2(2+)) = +28(4) kJ mol (-1). Pulsed gradient spin-echo (PGSE) NMR experiments provided the weighted-average hydrodynamic volume (VH) of the species present in CD 3CN solution at different copper concentrations (CCu). Nonlinear interpolation of VH as a function of C Cu for a dimer-monomer equilibrium led to the hydrodynamic volumes of both monomers (VH(0)(M)) and dimers (VH(0)(D)): VH(0)(a(+)) = 620(40) A(3), VH(0)(b(+)) = 550(10) A(3), VH(0)(a2(2+)) = 950(20) A(3), and VH(0)(b2(2+)) = 900(10) A(3). Cyclic voltammetry experiments performed in CH3CN and CH2Cl2 showed a quasi-reversible to irreversible behavior of the Cu(I)/Cu(II) redox couple for both complexes.

The N,N',O-heteroscorpionate ligand 1-(4-methoxy-3,5-dimethyl-pyridin-2-yl)-2-methyl-1-pyrazol-1-yl-propan-2-ol (LOH) was prepared in two high-yield steps. Complexes [M(LOH)2][MCl4] (M2+ = Cu2+ and Zn2+) and [M(LOH)2]Cl2 (M2+ = Ni2+ and Cu2+) were prepared and characterized by X-ray crystallography. The speciation in solution (methanol:water 95:5) of the M2+/LOH systems was investigated by means of spectrophotometric (Ni2+ and Cu2+) and 1H NMR (Zn2+) titrations. The beta1 and beta2 global formation constants for the [M(LOH)]2+ and [M(LOH)2]2+ species were obtained and are in agreement with the Irving-Williams series: Ni2+< Cu2+> Zn2+. The Zn2+/LOH system was studied by means of quantitative 1H-1H EXSY spectroscopy (300 K, mixing time = 0.2-0.8 s), which allows the description of the equilibria occurring between five octahedral [Zn(LOH)2]2+ structural isomers and tetrahedral [Zn(LOH)Cl]Cl species. Exchange constants kijex and associated rate constants kij suggest that two types of interconversion occur: octahedral-octahedral (faster) and octahedral-tetrahedral (slower). DFT calculations (B3LYP/6-311+G(d)) were employed to evaluate the relative stability of the [Zn(LOH)2]2+ isomers, which are comparable for the five complexes with a maximum energy difference of 6.3 kJ/mol.

The effect of the phenanthroline substituents on the structure and reactivity of platinum(II) and platinum(IV) complexes has been investigated. The X-ray crystal structures of the compounds [PtI(2)(4,7-Ph(2)phen)].CHCl(3) (1dz.CHCl(3)), [PtI(4)(4,7-Ph(2)phen)].CHCl(3) (2dz.CHCl(3)), [PtI(2)(2,9-Me(2)-4,7-Ph(2)phen)] (1fz), and [PtI(4)(2,9-Me(2)-4,7-Ph(2)phen)].I(2) (2fz.I(2)) have shown that complexes 1fz and 2fz, containing ortho-substituted phenanthrolines, exhibit a remarkable displacement of the equatorial iodine atoms from the N-Pt-N' plane (average 0.477(2) and 0.199(2) Å, respectively), a bending of the phenanthroline [angle between outer rings of 19.9(7) and 14.2(7) degrees, respectively] and a rotation of the N-C-C'-N' plane with respect to the N-Pt-N' plane [32.3(10) and 26.5(9) degrees, respectively]. Comparison between the structures of 1fz and 2fz, both having the phenanthroline with methyl substituents in the ortho position, indicates that, in the latter case, because of the presence of the two axial iodine ligands, the displacements of the ligands from the equatorial plane are smaller and find a compensation in a narrowing of the I(1)-Pt-I(1') angle (5 degrees ) and a lengthening of the Pt-N bonds (0.07 Å). The electrochemical behavior of the four-coordinate platinum(II) complexes shows that compounds possessing regular planar geometry have access to the one-electron reduced species, whereas those with distorted coordination geometry are irreversibly reduced by collapsing of the complex geometry. This is in sharp contrast with the behavior of related nickel complexes for which the pseudo-tetrahedral coordination imposed by bulky 2,9-substituents of phenanthroline stabilizes the nickel(I) species. Spectroscopic results allow us to assign a significant Pt(I) character to [1d](-) monoanions. The electrogenerated, plus one electron, complexes are not indefinitely stable and, because of conjugation with the phen ligand, progressively restore the Pt(II) oxidation state by transferring the electron to the peripheral organic ligand. The latter process can involve multiple electron additions in the macroelectrolysis time scale. The related platinum(IV) complexes [PtX(4)(L)] undergo irreversible two-electron reduction accompanied by fast release of the axial ligands and formation of the corresponding platinum(II) species.