| People | Locations | Statistics |
|---|---|---|
| Naji, M. |
| |
| Motta, Antonella |
| |
| Aletan, Dirar |
| |
| Mohamed, Tarek |
| |
| Ertürk, Emre |
| |
| Taccardi, Nicola |
| |
| Kononenko, Denys |
| |
| Petrov, R. H. | Madrid |
|
| Alshaaer, Mazen | Brussels |
|
| Bih, L. |
| |
| Casati, R. |
| |
| Muller, Hermance |
| |
| Kočí, Jan | Prague |
|
| Šuljagić, Marija |
| |
| Kalteremidou, Kalliopi-Artemi | Brussels |
|
| Azam, Siraj |
| |
| Ospanova, Alyiya |
| |
| Blanpain, Bart |
| |
| Ali, M. A. |
| |
| Popa, V. |
| |
| Rančić, M. |
| |
| Ollier, Nadège |
| |
| Azevedo, Nuno Monteiro |
| |
| Landes, Michael |
| |
| Rignanese, Gian-Marco |
|
Bond, Alan Maxwell
in Cooperation with on an Cooperation-Score of 37%
Topics
Publications (4/4 displayed)
- 2015Diminished electron transfer kinetics for [Ru(NH3)6]3+/2+, [α-SiW12O40]4-/5-, and [α-SiW12O40]5-/6- processes at boron-doped diamond electrodescitations
- 2015Changing the action of iron from stoichiometric to electrocatalytic in the hydrogenation of ketones in aqueous acidic mediacitations
- 2015Electroless deposition of iridium oxide nanoparticles promoted by condensation of [Ir(OH)6]2- on an anodized Au surface: application to electrocatalysis of the oxygen evolution reactioncitations
- 2015Redox levels of a closo-osmaborane: a density functional theory, electron paramagnetic resonance and electrochemical studycitations
Places of action
| Organizations | Location | People |
|---|
article
Redox levels of a closo-osmaborane: a density functional theory, electron paramagnetic resonance and electrochemical study
Abstract
A closo-type 11-vertex osmaborane [1-(η6-pcym)-1-OsB10H10] (pcym = para-cymene) has been synthesized and characterized by single-crystal X-ray diffraction and elemental analysis, as well as by 11B and 1H NMR, UV–visible, and mass spectrometry. The redox chemistry has been probed by dc and Fourier transformed ac voltammetry and bulk reductive electrolysis in CH3CN (0.10 M (n-Bu)4NPF6) and by voltammetry in the ionic liquid N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide (Pyrr1,4-NTf2), which allows the oxidative chemistry of the osmaborane to be studied. A single-crystal X-ray diffraction analysis has shown that [1-(η6-pcym)-1-OsB10H10] is isostructural with other metallaborane compounds of this type. In CH3CN (0.10 M (n-Bu)4NPF6), [1-(η6-pcym)-1-OsB10H10] undergoes two well-resolved one-electron reduction processes with reversible potentials separated by ca. 0.63–0.64 V. Analysis based on a comparison of experimental and simulated ac voltammetric data shows that the heterogeneous electron transfer rate constant (k0) for the first reduction process is larger than that for the second step at GC, Pt, and Au electrodes. k0 values for both processes are also larger at GC than metal electrodes and depend on the electrode pretreatment, implying that reductions involve specific interaction with the electrode surface. EPR spectra derived from the product formed by one-electron reduction of [1-(η6-pcym)-1-OsB10H10] in CH3CN (0.10 M (n-Bu)4NPF6) and electron orbital data derived from the DFT calculations are used to establish that the formal oxidation state of the metal center of the original unreduced compound is OsII. On this basis it is concluded that the metal atom in [1-(η6-pcym)-1-OsB10H10] and related metallaboranes makes a 3-orbital 2-electron contribution to the borane cluster. Oxidation of [1-(η6-pcym)-1-OsB10H10] coupled to fast chemical transformation was observed at 1.6 V vs ferrocene0/+ in Pyrr1,4-NTf2. A reaction scheme for the oxidation involving formation of [1-(η6-pcym)-1-OsB10H10]+, which rearranges to an unknown electroactive derivative, is proposed, and simulations of the voltammograms are provided.