Cobalt complexes with multiproton- and multielectron-responsive ligands are of interest for challenging catalytic transformations. The chemical and redox noninnocence of pentane-2,4-dione bis(-methylisothiosemicarbazone) (PBIT) in a series of cobalt complexes has been studied by a range of methods, including spectroscopy [UV-vis, NMR, electron paramagnetic resonance (EPR), X-ray absorption spectroscopy (XAS)], cyclic voltammetry, X-ray diffraction, and density functional theory (DFT) calculations. Two complexes [Co(HL)I]I and [Co()I] were found to act as precatalysts in a Wacker-type oxidation of olefins using phenylsilane, the role of which was elucidated through isotopic labeling.
View Article and Find Full Text PDFThe attenuated live bacterial vaccine strain Salmonella enterica Serovar Typhi Ty21a is the main constituent of Vivotif, the only licensed oral vaccine against typhoid fever. The strain was developed in the 1970s by chemical mutagenesis. In the course of this mutagenesis, a number of mutations were introduced into the vaccine strain.
View Article and Find Full Text PDFA C2-symmetric enantiopure 4,5-bis(pinene)-2,2'-bipyridine ligand (-)-L was used to investigate the diastereoselectivity in the formation of [ML3]2+ coordination species (M = Fe(II), Ru(II), Os(II), Zn(II), Cd(II), Cu(II), Ni(II)), and [ML2Cl2] (M = Ru(II), Os(II)). The X-ray structures of the [ML3]2+ complexes were determined for Delta-[FeL3](PF6)2, Delta-[RuL3](PF6)2, Lambda-[RuL3](PF6)2, Delta-[OsL3](PF6)2, and Lambda-[OsL3](TfO)2. All of these compounds were also characterized by NMR, CD and UV/VIS absorption spectroscopy.
View Article and Find Full Text PDFAsymmetric synthesis in coordination chemistry was described very clearly by Smirnoff in 1920, but, contrary to the development in organic chemistry, it was almost completely neglected for several decades. The interest in chirality in coordination chemistry (see the stereoview of [Ru(bpy) ] ) has increased rapidly in recent times as a consequence of developments in several fields where chirality is important (polynuclear systems, supramolecular structures, and enantioselective catalysis). Here we show many examples of how, through the choice of ligand, the configuration of a metal center or the chirality of a helicate can be predetermined.
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