Synthesis, structure and magnetic properties of chiral and nonchiral transition-metal malates

Carboxylate-bridged complexes of transition metals, M(II)=Mn(II), Fe(II), Co(II), Ni(II), Zn(II), were synthesised by reaction of M(II) salts with dl-malate and L-malate under hydrothermal conditions. These complexes form four series of compounds, which have been fully characterised structurally, thermally and magnetically. The crystal structures of the new chiral compounds, [Mn(L-mal)(H(2)O)] (1), [Fe(L-mal)(H(2)O)] (2), [Co(L-mal)(H(2)O)] (3) and [Zn(L-mal)(H(2)O)] (4) as well as those of the bimetallic analogues [Mn(0.63)Co(0.37)(L-mal)(H(2)O)] (5) and [Mn(0.79)Ni(0.21)(L-mal)(H(2)O)] (6) have been solved by single-crystal X-ray diffraction. The six L-malate monohydrates crystallise in the chiral space group P2(1)2(1)2(1) and consist in a three-dimensional network of metal(II) centres in octahedral sites formed by oxygen atoms. These structures were compared to those of the chiral trihydrate compounds [Co(L-mal)(H(2)O)]2 H(2)O (7), [Ni(L-mal)(H(2)O)]2 H(2)O (8) and [Co(0.52)Ni(0.48)(L-mal)(H(2)O)]2 H(2)O (9), which exhibit helical chains of M(II) centres, and those of dl-malate dihydrates [Co(dl-mal)(H(2)O)]H(2)O (10) and [Ni(dl-mal)(H(2)O)H(2)O (11) and trihydrate [Mn(L-mal)(H(2)O)]2 H(2)O (12) highlighting the great flexibility of the coordination by the malate ligand. UV/Vis spectroscopic results are consistent with octahedral coordination geometry of high-spin transition-metal centres. Extensive magnetic characterisation of each homologous series indicates rather weak coupling interaction between paramagnetic centres linked through carboxylate bridges. Curie-like paramagnetic, antiferromagnetic, ferromagnetic or weak ferromagnetic behaviour is observed and discussed on the basis of the structural features. The bimetallic compounds 5 and 6 represent new examples of chiral magnets.     

Synthesis and characterization of toluene-3,4-dithiolatoantimony(III) derivatives with some oxygen and/or sulphur donor ligands

Replacement reactions of toluene-3,4-dithiolatoantimony(III) chloride with oxygen and/or sulphur donor ligands like benzoic acid, thiobenzoic acid, thioacetic acid, phenol, thiophenol, sodium salicylate and thio glycolic acid in 1:1 molar ratio as well as disodium oxalate in 2:1 molar ratio in refluxing anhydrous benzene yielded toluene-3,4-dithiolatoantimony(III) mono oxo and/or thio carboxylic or phenolic derivatives of the general formula {R = OOCC₆H₅, SOCC₆H₅, SOCCH₃, OC₆H₅, SC₆H₅, OOCC₆H₄(OH) and SCH₂COOH} and

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These newly synthesized derivatives are yellow and brown solids/liquids and are soluble in common organic solvents like benzene, chloroform, dichloromethane, etc. These derivatives have been characterized by melting point determination, molecular weight determination, elemental analysis (C, H, S and Sb), spectral {UV, IR and NMR (¹H and ¹³C)} and thermal (TGA, DTA and DSC) studies.     

Short Total Synthesis of Ajoene

We describe a short total synthesis of ajoene, a major biologically active constituent of garlic. The instability of allicin as the only other known alternative starting material has led to the development of a reliable procedure for the synthesis of ajoene from simple building blocks that is also suitable for upscale operations.     

Transition-metal-catalyzed dehydrocoupling: a convenient route to bonds between main-group elements

The development of transition-metal-catalyzed dehydrocoupling reactions as a synthetic method for the formation of main-group element-element bonds provides an increasingly attractive and convenient alternative to traditional routes such as salt metathesis/elimination-type reactions. Since the first reported examples in the early 1980s, there has been a rapid expansion of this field, with extensions to a wide variety of metal-mediated homonuclear and heteronuclear bond-forming processes. Applications of this new chemistry in molecular and polymer synthesis, materials science, hydrogen storage and the transfer hydrogenation of organic substrates are attracting growing attention. An overview of this emerging area is presented in this Concepts article with a focus on recent results.     

Silver intercalation in PbS1.18(TiS2)n, n=1, 2, misfit layer compounds

The reaction between metallic Ag and PbS_1.18(TiS₂)_n, n=1, 2, misfit layer compounds has been investigated by electrochemical technique, X-ray powder analysis and transmission electron microscopy. It was found that silver intercalation is possible only in the compound with n=2. The thermodynamic behavior and location of phase boundaries were studied in the temperature range 400–650 K. DC-conductivity and magnetic-susceptibility measurements were performed, and the data can be interpreted as an appearance of small polarons during silver insertion.