Reduction electrochimique des oxydes de fer: Confrontation des caracteristiques electrochimiques et crist allographiques

Electrochemical properties of iron oxides, crystallographic data and examination of etching pits by scanning electron microscopy, suggest that ferric iron has electrochemical reactivity which differs according to its crystallographic position in the solid.     

Molecular Structure of the Ethylenediammonium Complex of a Tetracarboxy-macrocyclic Receptor Molecule

The crystal and molecular structure of the complex formed by the ionized bistartro-[18]-crown-6 receptor molecule 1 with the ethylenediammonium cation, is described. The macrocycle is roughly planar, the carboxy groups of each tartaric acid residue being in a diaxial relationship and extending above and below this plane. This conformation allows ‘lateral’ interactions with bound species to occur. The substrate is sandwiched between two macrocycles, with one of its NH heads anchored to the polyether core, and the other one in contact with the two carboxy groups of the neighboring molecule.     

Mechanism and kinetics of the catalytic CO-H2 reaction: An approach by chemical transients and surface relaxation spectroscopy

The aim of this paper is to demonstrate the importance of providing time-resolved information in catalysis research. Two truly in situ methods will be presented and compared for their merits and drawbacks: chemical transient kinetics (CTK) and pulsed field desorption mass spectrometry (PFDMS). The presentation will be given by way of example choosing the syngas (CO/H2) reaction over cobalt-based catalysts as a catalytic process. Despite numerous efforts in the past, the mechanism of this reaction is still under debate. In CTK the reaction is studied on a metal-supported catalyst under flow conditions in a pressure range extending from atmospheric pressure down to 100 Pa. Sudden changes in the partial pressures of the reactants then allow following the relaxation to either steady-state conditions ("transients") or cleanoff ("back transients"). In PFDMS short field pulses of several volts per nanometer are applied to a model catalyst which resembles a single metal particle grain (a "tip"). These pulses intervene during the ongoing reaction under flow conditions at pressures ranging from 10(-1) to 10(-5) Pa and cause field desorption of adsorbed species. This method is particularly suited to detect reaction intermediates in a time-dependent manner since the repetition frequency of the pulses can be systematically varied. It is shown that both methods lead to complementary results. While CTK allows conclusions on the mechanism of CO hydrogenation by following the time-dependent formation of hydrocarbon species, PFDMS provides insight into the initial steps leading to adsorbed CxHy species. A quantitative assessment of the CTK data allows the demonstration that the catalyst under working conditions is in an oxidized rather than metallic state. The initial steps to oxidation are also traced by PFDMS. Most importantly, however, CTK results allow formulation of a reaction mechanism that is common for both hydrocarbon and oxygenate formation and is based on the occurrence of a formate-type species as the most abundant surface intermediate.     

Methane activation by silica-supported Zr(IV) hydrides: the dihydride [(triple bond)SiO)2ZrH2] is much faster than the monohydride [(triple bond)SiO)3ZrH

The silica-supported Zr(iv) dihydride [(triple bond)SiO)2ZrH2] reacts quickly and completely with methane to yield [(triple bond)SiO)2ZrMe2] through the intermediate [(triple bond)SiO)2ZrHMe], while its monohydride analogue [(triple bond)SiO)3ZrH] yields the monomethylated product [(triple bond)SiO)3ZrMe] slowly and incompletely.     

Dynamic chemical devices: modulation of photophysical properties by reversible, ion-triggered, and proton-fuelled nanomechanical shape-flipping molecular motions

The terpy-derived (terpy=terpyridine) ligand 1 has an extended W shape in which the two appended photoactive pyrenyl groups are held apart. On binding of a zinc(II) ion with a terpy group, ligand 1 is converted into complex 2 whereby it adopts a U shape, thus stacking the aromatic units. This structural modification leads to a very pronounced change in photophysical properties: from a highly fluorescent free ligand to a very weakly emitting complex. The W/U structural switching can be reversibly induced by the addition of a competitive tren ligand, which binds and releases a zinc(II) ion under protonation/deprotonation cycles, thus leading to oscillations in light emission. Therefore, the present system performs periodic modulation of optical output through a nanomechanical shape-flipping motion, triggered by metal ion binding and fuelled by acid-base neutralisation energy. Overall, it represents an ion-triggered opto-mechanical supramolecular device.     

Protonic modulation of redox properties in ionisable [2 x 2] grid-like metalloarrays

The oxidation state of the cobalt centres can be controlled by modification of the protonation state in [2 x 2] grid-like arrays based on ionisable bis(hydrazone) ligands, allowing conversion of the paramagnetic Co(II)(4) into the diamagnetic Co(III)(4) grid.