Extraction of actinides with heterocyclic dicarboxamides

Extraction of actinides from aqueous nitric acid by three different heterocyclic dicarboxamides (2,6-pyridinedicarboxamide, 2,2′-bipyridine-6,6′-dicarboxamide and 1,10-phenanthroline-2,9-dicarboxamides) was studied. It was shown that all studied ligands extract actinides at different oxidation states (U(VI), Np(V), Pu(IV), Am(III), Cm(III)) from acidic solutions. All studied diamides extract Am(III) better than Cm(III). Et(pHexPh)ClPhen contains electron-withdrawing chlorine atoms at the positions 4 and 7 of the phenanthroline moiety (SF_Am/Cm = 4–6) and possesses the highest separation factor Am(III)/Cm(III). The studied ligands possess high extraction ability to all actinides present in HLW and therefore they could be used for simultaneous extraction of actinides in the GANEX-type process.     

Study of some volumetric and refractive properties of {PEG 300 (1) + ethanol (2)} mixtures at several temperatures

Molar volumes and excess molar volumes were investigated from measured density values for {PEG 300 (1) + ethanol (2)} binary mixtures at temperatures from 278.15 to 313.15 K. Both systems exhibit negative excess volumes probably due to increased interactions like hydrogen bonding and/or large differences in molar volumes of the components. Volume thermal expansion coefficients were also calculated for both binary mixtures and pure solvents. Refractive indices were also determined for all these non-aqueous mixtures and neat solvents at all temperatures. Furthermore, the Jouyban–Acree model was used for density, molar volume and refractive index correlations of the studied mixtures at different temperatures. The mean relative deviations between experimental and back-calculated density, molar volume and refractive index data were 0.07%, 0.99% and 0.01%, respectively.     

Enantioselective chemisorption on a chirally modified surface in ultrahigh vacuum: adsorption of propylene oxide on 2-butoxide-covered palladium(111)

The enantioselective chemisorption of (S)- and (R)-propylene oxide is measured on a Pd(111) surface chirally modified using (S)- and (R)-2-butanol. Reflection-absorption infrared spectroscopic (RAIRS) data suggest that adsorbed 2-butanol forms 2-butoxide species when heated to approximately 150 K and converts to a ketone with a concomitant loss in chirality at 200 K. Methyl ethyl ketone, ethylene, methane, CO, and hydrogen are found as products in temperature-programmed desorption (TPD). Propylene oxide adsorbs reversibly on Pd(111) at 80 K without undergoing any thermal decomposition, thus providing an ideal probe of surface chirality. The coverage of (R)-propylene oxide adsorbing on an (R)-2-butoxide-covered surface, ratioed to that on one covered by (S)-2-butoxide, reaches a maximum value of approximately 2 at a relative 2-butoxide coverage of approximately 25% of saturation and decreases to unity at a coverage of approximately 50% of saturation. This implies that the enantioselectivity depends critically on coverage and arises due to chiral "pockets" formed on the surface.     

Fast nitroxyl trapping by ferric porphyrins

Iron(II) porphyrin nitrosyl complexes are obtained in high yields from the reaction of iron(III) porphyrins with the nitroxyl donors sodium trioxodinitrate and toluensulfohydroxamic acid. The reaction was found to proceed both in organic solvents and in aqueous media from iron(III) (meso-tetraphenyl) porphyrinate ([FeIII(TPP)]+) and iron(III) meso-tetrakis (4-sulfonatophenyl) porphyrinate ([FeIII(TPPS)]3-) or iron(III) protoporphyrin IX, respectively. The kinetic rate constant for the reaction of ([FeIII(TPPS)]3-) with sodium trioxodinitrate (kon) was estimated to be 1.00 +/- 0.04 x 107 M-1 s-1. As well as resulting in a versatile method for obtaining ferrous nitrosyl porphyrins, the reaction points at ferric porphyrins as efficient nitroxyl traps and provides a tool to model nitroxyl reactivity toward hemeproteins.     

Discrimination of nitroxyl and nitric oxide by water-soluble Mn(III) porphyrins

The water-soluble manganese(III) meso-tetrakis (N-ethylpyridinium-2-yl) porphyrin (Mn(III)TEPyP) and manganese(III) meso-(tetrakis(4-sulfonato-phenyl)) porphyrinate (Mn(III)TPPS) are able to chemically distinguish between HNO and NO donors, reacting with the former in a fast, efficient, and selective manner with concomitant formation of the {MnNO}(7) complex (k(on(HNO)) approximately equal to 10(5) M(-1) s(-1)), while they are inert or react very slowly with NO donors. DFT calculations and kinetic data suggest that HNO trapping is operative at least in the case of Mn(III)TPPS, while catalytic decomposition of the HNO donors (sodium trioxodinitrate and toluene sulfohydroxamic acid) seems to be the main pathway for Mn(III)TEPyP. In the presence of oxygen, the product Mn(II)TEPyP(NO) oxidizes back to Mn(III)TEPyP, making it possible to process large ratios of nitroxyl donor with small amounts of porphyrin.     

Structure and Bonding in Pentacyano(L)ferrate(II) and Pentacyano(L)ruthenate(II) Complexes (L = Pyridine, Pyrazine, and N-Methylpyrazinium): A Density Functional Study

Density Functional Theory (DFT) at the generalized gradient approximation (GGA) level has been applied to the complexes [Fe(CN)(5)L](n-) and [Ru(CN)(5)L](n-) (L = pyridine, pyrazine, N-methylpyrazinium), as well as to [Fe(CN)(5)](3)(-) and [Ru(CN)(5)](3)(-). Full geometry optimizations have been performed in all cases. The geometrical parameters are in good agreement with available information for related systems. The role of the M(II)-L back-bonding was investigated by means of a L and cyanide Mulliken population analysis. For both Fe(II) and Ru(II) complexes the metal-L dissociation energies follow the ordering pyridine < pyrazine < N-methyl pyrazinium, consistent with the predicted sigma-donating and pi-accepting abilities of the L ligands. Also, the computed metal-L bond dissociation energies are systematically smaller in the Ru(II) than in the Fe(II) complexes. This fact suggests that previous interpretations of kinetic data, showing that ruthenium complexes in aqueous solution are more inert than their iron analogues, are not related to a stronger Ru-L bond but are probably due to solvation effects.     

Binuclear copper(II) oxidation products from copper(I) complexes with tridentate ligands. Magnetostructural characterization

The bis-pyridine tridentate ligands (6-R-2-pyridylmethyl)-(2-pyridylmethyl) benzylamine (RDPMA, where R = CH(3), CF(3)), (6-R-2-pyridylmethyl)-(2-pyridylethyl) benzylamine (RPMPEA, where R = CH(3), CF(3)), and the bidentate ligand di-benzyl-(6-methyl-2-pyridylmethyl)amine (BiBzMePMA) have been synthesized and their copper(I) complexes oxidized in a methanol solution to afford self-assembled bis-micro-methoxo-binuclear copper(II) complexes (1, 2, 4, 6) or hydroxo- binuclear copper(II) complexes (3). Oxidation of the nonsubstituted DPMA (R = H) in dichloromethane gives a chloride-bridged complex (5). The crystal structures for [Cu(MeDPMA)(MeO)](2)(ClO(4))(2) (1), [Cu(RPMPEA)(MeO)](2)(ClO(4))(2) (for 2, R= Me, and for 4, R = CF(3)), [Cu(BiBzMePMA)(MeO)](2)(ClO(4))(2) (6), [Cu(FDPMA)(OH)](2)(ClO(4))(2) (3), and [Cu(DPMA)(Cl)](2)(ClO(4))(2) (5) have been determined, and their variable-temperature magnetic susceptibility has been measured in the temperature range of 10-300 K. The copper coordination geometries are best described as square pyramidal, except for 6, which is square planar, because of the lack of one pyridine ring in the bidentate ligand. In 1-4 and 6, the basal plane is formed by two pyridine N atoms and two O atoms from the bridging methoxo or hydroxo groups, whereas in 5, the bridging Cl atoms occupy axial-equatorial sites. Magnetic susceptibility measurements show that the Cu atoms are strongly coupled antiferromagnetically in the bis-methoxo complexes 1, 2, 4, and 6, with -2J > 600 cm(-)(1), whereas for the hydroxo complex 3, -2J = 195 cm(-)(1) and the chloride-bridged complex 5 shows a weak ferromagnetic coupling, with 2J = 21 cm(-)(1) (2J is an indicator of the magnetic interaction between the Cu centers).     

Micellization of monomeric and dimeric (gemini) surfactants in polar nonaqueous-water-mixed solvents

Dimeric or gemini surfactants are novel surfactants that are finding a great deal of discussion in the academic and industrial arena. They consist of two hydrophobic chains and two polar head groups covalently linked by a spacer. Data on critical micelle concentration (cmc) and degree of counterion dissociation (α) are reported on bis-cationic C₁₆H₃₃N⁺(CH₃)₂–(CH₂)_s–N⁺(CH₃)₂C₁₆H₃₃, 2Br⁻, referred to as 16-s-16, for spacer lengths s=4, 5, 6 in aqueous and in polar nonaqueous (1-propanol, 2-methoxyethanol or methyl cellosolve, dimethyl sulfoxide, acetonitrile)-water-mixed solvents. The behavior is compared with conventional monomeric surfactant cetyltrimethylammonium bromide (CTAB). Thermodynamic parameters are obtained from the temperature dependence of the cmc values. It is observed that micellization tendency of the surfactants decreases in the presence of polar nonaqueous solvents. However, detailed studies with dimethylsulfoxide (DMSO) show that the geminis nearly outclass the micellization-arresting property of this solvent. Also, within geminis, higher spacer length is found suitable for showing micellization even with high DMSO content (50% v/v). The implications of these results of gemini micellization may be useful in micellar catalysis in polar nonaqueous solvents.     

The Synthesis of Naphthosultine and Benzodisultines and Their Pyrolysis with Dienophiles: Studies on o‐Naphthoquinodimethane and Bis‐o‐Quinodimethane

Sealed tube reactions of the naphthosultine 8 with a series of electron‐deficient dienophiles (fumaronitrile, N‐phenylmaleimide, dimethyl fumarate, and dimethyl acetylenedicarboxylate) in toluene at 180 °C gave corresponding 1:1 cycloadducts 11–14 in various amounts along with rearranged naphthosulfolene 7 in 67–95% yields. The reaction of 1,2,4,5‐tetra(bromomethyl)benzene with Rongalite (sodium form aldehyde sulfoxylate) and tetrabutylammonium bromide in DMF gave benzodisultines 17 and 18 in a combined yield of 56%. Sealed tube reactions of benzodisultines 17 and 18 with a series of dienophiles in xylene at 200 °C gave corresponding 1:1 and 1:2 cycloadducts 20–27 . The results suggested that thermal extrusion of sulfurdioxide from these sultines led to either o‐naphthoquinodimethane 6 (from 8 ) or bis‐o‐quinodimethane 19 (from 17 and 18 ); sub sequent trapping of these reactive intermediates by dienophiles and SO₂ gave various 1:1 and 1:2 Diels‐Alder ad ducts in modest to excellent yields.