Proton and Electron Transfer to a Polymer‐Supported Nitrido Molybdenum(VI) Complex

Invited for the cover of this issue is the group of Katja Heinze at Johannes Gutenberg University of Mainz, Germany. The cover image shows the reactive imido molybdenum(V) intermediate that has been obtained by protonation followed by reduction of the nitrido molybdenum(VI) precursor anchored to a polymeric environment.

Proton and Electron Transfer to a Polymer‐Supported Nitrido Molybdenum(VI) Complex (Eur. J. Inorg. Chem. 36/2013)

Porphyrin amino acids-amide coupling, redox and photophysical properties of bis(porphyrin) amides.

New trans-AB2C meso-substituted porphyrin amino acid esters with meso-substituents of tunable electron withdrawing power (B = mesityl, 4-C6H4F, 4-C6H4CF3, C6F5) were prepared as free amines 3a-3d, as N-acetylated derivatives Ac-3a-Ac-3d and corresponding zinc(II) complexes Zn-Ac-3a-Zn-Ac-3d. Several amide-linked bis(porphyrins) with a tunable electron density at each porphyrin site were obtained from the amino porphyrin precursors by condensation reactions (4a-4d) and mono- and bis(zinc(II)) complexes Zn(2)-4d and Zn(1)Zn(2)-4d were prepared. The electronic interaction between individual porphyrin units in bis(porphyrins) 4 is probed by electrochemical experiments (CV, EPR), electronic abso…

Überoxidation als Schlüsselschritt im Mechanismus der MoCl5 - vermittelten dehydrierenden Arenkupplung

Over-Oxidation as the Key Step in the Mechanism of the MoCl5-Mediated Dehydrogenative Coupling of Arenes.

Molybdenum pentachloride is an unusually powerful reagent for the dehydrogenative coupling of arenes. Owing to the high reaction rate using MoCl5, several labile moieties are tolerated in this transformation. The mechanistic course of the reaction was controversially discussed although indications for a single electron transfer as the initial step were found recently. Herein, based on a combined study including synthetic investigations, electrochemical measurements, EPR spectroscopy, DFT calculations, and mass spectrometry, we deduct a highly consistent mechanistic scenario: MoCl5 acts as a one-electron oxidant in the absence of TiCl4 and as two-electron oxidant in the presence of TiCl4, bu…

Gold(iii) tetraarylporphyrin amino acid derivatives: ligand or metal centred redox chemistry?

EPR spectroscopy and DFT calculations show that the site of reduction of porphyrinato gold(iii) complexes depends on the counterions X, the meso substituents R and the solvent.

Thermal and Photoinduced Electron Transfer in Directional Bis(terpyridine)ruthenium(II)–(Bipyridine)platinum(II) Complexes

Metalloligands L1 and L2 consisting of directional bis(terpyridine)ruthenium(II) units and bipyridine moieties were constructed by amide formation. From these metalloligands two Ru–Pt heterobimetallic complexes 1 and 2 were derived by a building-block method by means of platination with [PtCl2(dmso)2]. Both bimetallic complexes 1 and 2 feature metal-to-ligand charge transfer (MLCT) absorptions, and emission occurs at room temperature in fluid solution from 3MLCT(Ru) states in all cases. Energy transfer from platinum to ruthenium is observed in 2 but not in 1 (light harvesting). The one-electron-reduced species [1]– and [2]– were prepared by reduction of 1 and 2 with decamethylcobaltocene. E…

CCDC 934080: Experimental Crystal Structure Determination

Related Article: Anica Wünsche von Leupoldt, Christoph Förster, Tobias J. Fiedler, Nicolas H. Bings, Katja Heinze|2013|Eur.J.Inorg.Chem.||6079|doi:10.1002/ejic.201301156

CCDC 959158: Experimental Crystal Structure Determination

Related Article: Anica Wünsche von Leupoldt, Christoph Förster, Tobias J. Fiedler, Nicolas H. Bings, Katja Heinze|2013|Eur.J.Inorg.Chem.||6079|doi:10.1002/ejic.201301156

CCDC 930315: Experimental Crystal Structure Determination

Related Article: Anica Wünsche von Leupoldt, Christoph Förster, Tobias J. Fiedler, Nicolas H. Bings, Katja Heinze|2013|Eur.J.Inorg.Chem.||6079|doi:10.1002/ejic.201301156