The solvolysis oftrans-[Co(4-Mepy)4Cl2]ClO4 in water-methanol mixtures

Summary The solvolysis of thetrans-[Co(4-Mepy)₄Cl₂]ClO₄ complex was studied in 0 to 70% v/v H₂O: MeOH mixtures at 40, 45, 50 and 55 °C. The high negative S^* values found for the complex cation under investigation, relative to that oftrans- [Co(py)₄Cl₂]⁺ reported in the literature, were attributed to the substituent methyl groups. The free energies of transfer of both the ground and the transition states were calculated from which the dominant effect of the solvent on the transition state is apparent.     

Synthesis and Characterization of Heteropolynuclear Redox Active Materials[FerCuCl]4YY′; Y?=?Y′?=?O, Y?=?Y′?=?Cat and Y?=?O, Y′?=?Cat, Fer?=?N,N-dimethylaminomethylferrocene and Cat?=?3,4,5,6-tetrachlorocatecholato Ligand

This paper describes the synthesis and characterization of heteropolynuclear redox active materials [FerCuCl]₄YY′, Y = Y′ = O, Y = Y′ = Cat and Y = O, Y′ = Cat, Fer = N,N-dimethylaminomethylferrocene and Cat = 3,4, 5,6-tetrachlorocatecholato ligand. Manometric O₂ uptake measurements in PhNO₂ show that tetranuclear [FerCuCl]₄ and [FerCuCl]₄Cat give the tetranuclear oxocopper(II) products [FerCuCl]₄O₂ and [FerCuCl]₄CatO, respectively. The absence of carbonyl stretching vibrational bands in [FerCuCl]₄Cat₂ and [FerCuCl]₄CatO suggest that tetrachloro-1,2-benzoquinone (TClBQ) is reduced to the corresponding catecholete during the oxidation of copper(I) centers in [FerCuCl]₄. The near i.r. electronic spectra for [FerCuCl]₄O₂, [FerCuCl]₄CatO and [FerCuCl]₄Cat₂ exhibit broad intense split maxima in the 750–875 nm range, attributed to a minimum of three halide ligands per Cu. Room temperature solid state e.p.r. spectra for [FerCuCl]₄CatO and [FerCuCl]₄Cat₂ are of the axial type, suggesting a square pyramidal geometry around Cu^II.     

Acyclic chiral amines and amino acids as inexpensive and readily tunable catalysts for the direct asymmetric three-component Mannich reaction

The direct three-component asymmetric Mannich reaction catalyzed by acyclic chiral amines or amino acids is presented. Simple acyclic chiral amines and amino acids--such as alanine-tetrazole (9), alanine, valine, and serine-catalyzed the three-component asymmetric Mannich reactions between unmodified ketones, p-anisidine, and aldehydes with high chemo- and stereoselectivity, furnishing the corresponding Mannich bases with up to >99 % ee. This study demonstrates that the whole range of amino acids in nature, as well as nonproteogenic amino acid derivatives, can be considered in the design and tuning of novel, inexpensive organocatalysts for the direct asymmetric Mannich reaction.     

Formation and characterization of asymmetric nanofiltration membrane: Effect of shear rate and polymer concentration

In this study, we report the effects of shear rates and polymer concentrations in the formation of asymmetric nanofiltration membrane using a simple dry/wet phase inversion technique. Employing the combination of irreversible thermodynamic model, solution-diffusion model (Spiegler–Kedem equation), steric-hindrance pore (SHP) model and Teorell–Meyers (TMS) model, the transport mechanisms and membrane structural properties were determined and have been characterized for different cases of those formation parameters. The experimental and modeling showed very promising results in terms of membrane performance with interesting structural details. The optimum shear rate (critical shear rate) was found to be at about 203.20 s⁻¹ and the best polymer concentration toward the formation of high performance nanofiltration membrane is in the range of 19.60–23.10%. The modeling results suggested that the pore radius of the membranes produced lies within the range of pore radius of 29 commercial available membranes. This study also proposed that the electrolytes transport through nanofiltration membrane was dominated by a convection factor which accounted approximately 30% more than a diffusion factor. This study also indicated that shear rate and polymer concentration were found to affect the membrane performance and structural properties by providing, to a certain extent, an oriented membrane skin layer which in turn exhibiting an improvement in membrane separation ability.     

Studies on some cadmium mixed ligand complexes using differential pulse polarography

Differential pulse polarography was used to study the mixed ligand complexes of imidazole and some dicarboxylate anions namely, oxalate, tartrate and malonate with Cd(II) at constant ionic strength (mu = 1, NaNO(3)) at 25 +/- 0.1 degrees . It has been found that the reduction of complexes is reversible and diffusion-controlled. Three mixed complexes are formed with malonate (or oxalate) whereas four mixed complexes are formed with tartrate. The overall stability constants for each system were calculated and discussed.     

Ruthenium(II) <Emphasis Type="Italic">N</Emphasis>-heterocyclic Carbene Complexes in the Transfer Hydrogenation of Ketones

Six ruthenium-N-heterocyclic carbene complexes (2–7) have been prepared and the new compounds characterized by C, H, N analyses, ¹H-n.m.r. and ¹³C-n.m.r. The reduction of ketones to alcohols via transfer hydrogenation was achieved with catalytic amounts of complexes (2–7) in the presence of t-BuOK.     

Ultrafast decay of electronically excited singlet cytosine via a pi,pi* to n(O),pi* state switch

Singlet fluorescence lifetimes of adenosine, cytidine, guanosine, and thymidine, determined by femtosecond pump-probe spectroscopy (Pecourt, J.-M. L.; Peon, J.; Kohler, B. J. Am. Chem. Soc. 2000, 122, 9348. Pecourt, J.-M. L.; Peon, J.; Kohler, B. J. Am. Chem. Soc. 2001, 123, 10370), show that the excited states produced by 263 nm light in these nucleosides decay in the subpicosecond range (290-720 fs). Ultrafast radiationless decay to the ground state greatly reduces the probability of photochemical damage. In this work we present a theoretical study of isolated cytosine, the chromophore of cytidine. The experimental lifetime of 720 fs indicates that there must be an ultrafast decay channel for this species. We have documented the possible decay channels and approximate energetics, using a valence-bond derived analysis to rationalize the structural details of the paths. The mechanism favored by our calculations and the experimental data involves (1) a two-mode decay coordinate composed of initial bond length inversion followed by internal vibrational energy redistribution (IVR) to populate a carbon pyramidalization mode, (2) a state switch between the pi,pi* and nO,pi* (excitation from oxygen lone pair) excited states, and (3) decay to the ground state through a conical intersention. A second decay path through the nN,pi* state (excitation from the nitrogen lone pair), with a higher barrier, involves out-of-plane bending of the amino substituent.     

An efficient synthesis of 5,5′-diaryl-2,2′-bichalcophenes

A convenient and high yielding synthesis of 5,5′-diaryl-2,2′-bichalcophenes (furans, thiophenes, and selenophenes) by the hexabutylditin-mediated homocoupling of 5-bromochalcophenes is described. This approach has been applied to the synthesis of the blue-light-emitting compound 5,5′-bis(4-aminophenyl)-2,2′-bifuryl (PFDA).     

Synthesis and characterization of new macrocyclic Schiff base derived from 2,6-diaminopyridine and 1,7-bis(2-formylphenyl)-1,4,7-trioxaheptane and its Cu(II), Ni(II), Pb(II), Co(III) and La(III) complexes

A new macrocyclic ligand, 1,3,5-triaza-2,4:7,8:16,17-tribenzo-9,12,15-trioxacyclooktadeca-1,5-dien (L) was synthesized by reaction of 2,6-diaminopyridine and 1,7-bis(2-formylphenyl)-1,4,7-trioxaheptane. Then, its Cu(II), Ni(II), Pb(II), Co(III) and La(III) complexes were synthesized by template effect by reaction of 2,6-diaminopyridine and 1,7-bis(2-formylphenyl)-1,4,7-trioxaheptane and Cu(NO₃)₂ · 3H₂O, Ni(NO₃)₂ · 6H₂O, Pb(NO₃)₂, Co(NO₃)₂ · 6H₂O, La(NO₃)₃ · 6H₂O, respectively. The ligand and its metal complexes have been characterized by elemental analysis, IR, ¹H and ¹³C NMR, UV–Vis spectra, magnetic susceptibility, thermal gravimetric analysis, conductivity measurements, mass spectra and cyclic voltammetry. All complexes are diamagnetic and Cu(II) complex is binuclear. The Co(II) was oxidized to Co(III). The comparative electrochemical studies show that the nickel complex exhibited a quasi-reversible one-electron reduction process while copper and cobalt complexes gave irreversible reduction processes in DMSO solution.     

Solvent effects on the initial and transition states upon solvolysis oftrans-dichlorotetra(4-ethylpyridine)cobalt(III) perchlorate in water+methanol mixtures

Summary The solvolysis of trans-[Co(4-Etpy)₄Cl₂]⁺ (1) (Etpy=ethylpyridine) was investigated in water and in a wide range of water+methanol mixtures. The effect of temperature on the solvolysis was considered and the thermodynamic parameters of activation were calculated. The free energies of transfer of (1) in the initial state were calculated from the solubility of the complex [Co(4-Etpy)₄Cl₂]₂[ReCl₆]. The free energy of transfer of the cation (1) in the transition state was calculated using a free energy cycle. The effect of the solvent structure on (1) is dominant in the transition state, where –G _t ^o (1) transition >–G _t ^o (1) initial. Comparison of the present thermodynamic data with those obtained previously fortrans-[Co(4-Mepy)₄Cl₂]⁺, (2), andtrans-[Co(py₄Cl₂]⁺, (3) in the same solvent mixture, shows that the stability increases in the order: (1), (2)<(3) at low mole fraction of the co-solvent, contrary to expectation, while at high mole fraction the order of increasing stability is: (1)<(3)<(2). The results were interpreted on non-electrostatic grounds.