Search results for "Dati"

Controlled thermal oxidation of nanostructured vanadium thin films

2016

Abstract Pure V thin films were dc sputtered with different pressures (0.4 and 0.6 Pa) and particle incident angles α of 0°, 20° and 85°, by using the GLancing Angle Deposition (GLAD) technique. The sputtered films were characterized regarding their electrical resistivity behaviour in atmospheric pressure and in-vacuum conditions as a function of temperature (40–550 °C), in order to control the oxidation process. Aiming at comprehending the oxidation behaviour of the samples, extensive morphological and structural studies were performed on the as-deposited and annealed samples. Main results show that, in opposition to annealing in air, the columnar nanostructures are preserved in vacuum con…

Spectroscopic study of the electric field induced valence change of Fe-defect centers in SrTiO(3)

2011

The electrochemical changes induced by an electric field in Fe-doped SrTiO(3) have been investigated by X-ray absorption spectroscopy (XANES and EXAFS), electron paramagnetic resonance (EPR) and Raman spectroscopy. A detailed study of the Fe dopant in the regions around the anode and cathode reveals new insights into the local structure and valence state of Fe in SrTiO(3) single crystals. The ab initio full multiple-scattering XANES calculations give an evidence of the oxygen vacancy presence in the first coordination shell of iron. Differences in the length and disorder of the Fe-O bonds as extracted from EXAFS are correlated to the unequivocal identification of the defect type by compleme…

Catalytic epoxidation using dioxidomolybdenum(VI) complexes with tridentate aminoalcohol phenol ligands

2019

Reaction of the tridentate aminoalcohol phenol ligands 2,4-di-tert-butyl-6-(((2 hydroxyethyl)(methyl)amino)methyl)phenol (H2L1) and 2,4-di-tert-butyl-6-(((1-hydroxybutan-2-yl)amino)methyl)phenol (H2L2) with [MoO2(acac)2] in methanol solutions resulted in the formation of [MoO2(L1)(MeOH)] (1) and [MoO2(L2)(MeOH)] (3), respectively. In contrast, the analogous reactions in acetonitrile afforded the dinuclear complexes [Mo2O2(μ-O)2(L1)2] (2) and [Mo2O2(μ-O)2(L2)2] (4). The corresponding reactions with the potentially tetradentate ligand 3-((3,5-di-tert-butyl-2-hydroxybenzyl)(methyl)amino)propane-1,2-diol (H3L3) led to the formation of the mononuclear complex [MoO2(L3)(MeOH)] (5) in methanol whi…

Iminium Catalysis (n → π*)

2016

Switching and redox isomerism in first-row transition metal complexes containing redox active Schiff base ligands.

2014

International audience; The reversible redox isomerisms in first row transition metal complexes of the type ML2 were studied. The six ML2 complexes (M = Mn(III) (), Fe(II) (), Co(III) (), Ni(II) (), Cu(II) () and Zn(II) ()) were synthesized with a redox active Schiff base ligand [2-(3,5-di-tert-butyl-2-hydroxyphenylamino)-4-chlorophenol] (H3L) presenting different oxidation states from -2 to 0 (L(2-), L(-) and L(0)). EPR spectra and magnetic susceptibility measurements indicate the presence of complexes of the type [Mn(III)(L(2-))(L(-))] () with S = 1/2, [Fe(II)(L(-))2] () with S = 2, [Co(III)(L(2-))(L(-))] () with S = 1/2, [Ni(II)(L(-))2] () with S = 1, [Cu(II)(L(-))2] () with S = 1/2 and …

Electrochemical Fluorocyclization of N-Allylcarboxamides to 2-Oxazolines by Hypervalent Iodine Mediator

2018

A resource saving protocol for the synthesis of 5-fluoromethyl-2-oxazolines by using electrochemistry has been realized. Thereby, a hypervalent iodine species I(III) is generated by anodic oxidation in the presence of Et3N·5HF and mediates the cyclization of N-allylcarboxamide to 5-fluoromethyl-2-oxazoline. This method allows application to various substrates furnishing the 2-oxazolines with yields up to 68%. The protocol is easy to conduct under constant current conditions offering a sustainable alternative over conventional reagent-based pathways.

Computational study of the spin-forbidden H 2 oxidative addition to 16-electron Fe(0) complexes

2003

International audience; The spin-forbidden oxidative addition of H2 to Fe(CO)4, Fe(PH3)4, Fe(dpe)2 and Fe(dmpe)2 [dpe = H2PCH2CH2PH2, dmpe = (CH3)2PCH2CH2P(CH3)2] has been investigated by density functional theory using a modified B3PW91 functional. All 16-electron fragments are found to adopt a spin triplet ground state. The H2 addition involves a spin crossover in the reagents region of configurational space, at a significantly higher energy relative to the triplet dissociation asymptote and, for the case of Fe(CO)4·H2, even higher than the singlet dissociation asymptote. After crossing to the singlet surface, the addition proceeds directly to the classical cis-dihydride product. Only for…

NMR T1-Relaxation Measurements on Paramagnetic Organolanthanides: An Alternative Tool for Structure Determination in Solution

2005

1H NMR investigations were conducted on four paramagnetic organolanthanides, all bearing the tetraisopropylcyclopentadienyl ligand Cp4i (HC5iPr4) in order to verify whether or not interactions observed in the solid state are maintained in solution. In some cases variable-temperature experiments were necessary to enhance the resolution and determine the best conditions for the study. The 1D NMR spectrum could be interpreted in every case. Complementary 2D COSY experiments allowed the full attribution of the signals. T1 (1H) relaxation values were determined for all the paramagnetic complexes at the most suitable temperature, and compared with those of the diamagnetic KCp4i. The same tendency…

Mild, Fast, and Easy To Conduct MoCl5-Mediated Dehydrogenative Coupling Reactions in Flow

2018

A convenient and straightforward approach to performing oxidative coupling reactions in flow is presented. A collection of electron-rich benzene derivatives was subjected to this protocol, and the distinct utility of molybdenum pentachloride (MoCl5) is established. Using this unexplored protocol, biphenyls could be obtained in 21–91% isolated yield. This simple protocol opens a new chapter in reagent-mediated dehydrogenative coupling reactions, and yields are compared to classical approaches.

Green synthesis of cavity-containing manganese oxides with superior catalytic performance in toluene oxidation

2019

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