Search results for "Disproportionation"
showing 10 items of 26 documents
Imidotungsten(VI) complexes with chelating amino and imino phenolates
2011
The reaction of WOCl(4) with 2,4-di-tert-butyl-6-((isopropylamino)methyl)phenol followed by the reaction with phenyl isocyanate leads to the formation of imidotungsten(VI) complex [W(NPh)Cl(3)(OC(6)H(3)(CH(2)NH-i-Pr)-2-t-Bu(2)-4,6)] 4 with a chelating aminophenolate ligand. When the same procedure was applied using aminophenols with bulkier substituents in the amino group, the final product was an unexpected Schiff-base complex [W(NPh)Cl(3)(OC(6)H(3)(CH=NPh)-2-t-Bu(2)-4,6)] 5, where the ligand is derived from 2,4-di-tert-butyl-6-((phenylimino)methyl)phenol. Complex 5 is also formed in the thermal degradation of 4. On the whole, 5 appears to be formed by a disproportionation of intermediate …
Titanium and zirconium complexes that contain a tridentate bis(phenolato) ligand of the [OOO]-type
2003
Abstract The oxygen-linked bis(phenol) 2-oxapropanediyl-1,3-bis(2-tert-butyl-4-methylphenol), [OOO]H2, was prepared in good yield by the condensation of 2-tert-butyl-6-hydroxymethyl-4-methylphenol at 155 °C. This bis(phenol) reacted cleanly with titanium tetrachloride to give the orange titanium dichloro complex [OOO]TiCl2 in virtually quantitative yield. The solubility in pentane indicates a monomeric structure for [OOO]TiCl2 in solution. The reaction of titanium tetra(isopropoxide) gave the di(isopropoxy) complex [OOO]Ti(OiPr)2 which also adopts a monomeric structure of C2v-symmetry in solution. The reaction of the dichloro complex [OOO]TiCl2 with benzyl Grignard reagent in diethyl ether …
High Turnover Catalase Activity of a Mixed‐Valence Mn II Mn III Complex with Terminal Carboxylate Donors
2015
The neutral dimanganese(II,III) complex [Mn-2(BCPMP)-(OAc)(2)] [1; BCPMP3- = 2,6-bis({(carboxymethyl)[(1-pyridyl)-methyl] amino} methyl)-4-methylphenolato] has been synthesized and characterized. The complex contains two terminal carboxylate donors. Complex 1 was found to be an effective catalyst for the disproportionation of H2O2 with high catalytic rate and a turnover number of 7500, the highest turnover reported to date for a catalase mimic. The rates and TON were significantly higher than recorded for a dicationic dimanganese( II,III) counterpart ([Mn-2(BPBP)(OAc)(2)]center dot(ClO4)(2), 2; BPBP- = 2,6-bis{[bis(2-pyridylmethyl)amino]methyl}-4-butylphen-olato), which lacks the terminal c…
An electrochemical process to prepare and recycle biobased ionic liquids
2019
This manuscript describes the first electrosynthesis of biobased ionic liquids from L-valine, oxalic acid and glyoxal, which is energy-efficient, does not emit toxic waste and avoids the formation of inorganic waste. These ionic liquids were then used in the development of our electro-recycling process. While their recycling yields are still moderated due to recombination and disproportionation reactions, this unprecedented recycling technology is very promising in terms of environmental and economic gains. Indeed, it has a high energy efficiency, requires low cost equipment, allows a strong decrease of the price of such ionic solvents, limits the use of non-renewable resources and solves t…
Electrochemical and Spectroelectrochemical Behavior of a Tetracyanotriphenodioxazine in Solution and Thin-Films
2018
International audience; We report the electrochemical behavior of a tetracyano triphenodioxazine bearing two triisopropylsilylethynyl moieties (TiPS‐TPDO‐tetraCN) during its reduction studied either in solution or after vacuum evaporation deposition on indium tin oxide (ITO) support. While in dichloromethane, it typically proceeds in two successive monoelectronic reactions, in acetonitrile, the mechanism appears more complex. Fine analysis of the spectroelectrochemical results combined with simulation of the voltammograms with various amount of water suggest the involvement of water and of a restructured dianion in the electrochemical process. In the solid‐state, the formation of the diprot…
Control of catalytic properties of ZSM-5 made by fast and template- free synthesis.
1989
Abstract The fast template-free synthesis of ZSM-5 was accomplished in both static and stirred autoclaves employing sodiumwaterglass.silica hydrogel and pyrogenic silicas as silica sources. Highly pure crystalline ZSM-5 was obtained in the sodiumwaterglass reaction system in the stirred autoclaves without seeds within 3 hours. Addition of 2% (w/w) of seeds reduced the reaction time to 2 hours. The catalytic activity and shape selectivity of the H-ZSM-5, tested by the disproportionation of ethylbenzene, was found to be largely controlled by the synthesis parameters and by the posttreatments. The homogeneous aluminum distribution across the crystals achieved by this synthetis route resulted i…
Integrated experimental and computational spectroscopy study on the protonation of the α-nitronyl nitroxide radical unit
2011
The stability of the α-nitronyl nitroxide radical unit under acidic conditions is investigated by an integrated experimental UV/Vis spectroscopy and TDDFT study. In the field of molecular magnetism, α-nitronyl nitroxide radicals are important as purely organic spin carriers due to their synthetic versatility. Here, the existence of an intermediate of the protonated α-nitronyl nitroxide radical unit is demonstrated for the first time and a proposed disproportionation reaction is confirmed.
Isomerization and disproportionation of m-xylene in a zeolite with 9- and 10-membered ring pores: Molecular dynamics and catalytic studies
2006
The unique pore topology of zeolite ITQ-13 with 9-membered ring (MR) channels intersected by perpendicular 10-MR channels and larger void space with 10-MR cross-sections was studied for meta-xylene isomerization and disproportionation. Product distribution was interpreted on the basis of pore topology and compared with zeolites with 12-MR (β), 10-MR, and intersecting 12-MR cavities (NU-87), as well as 10-MR (ZSM-5) zeolites. The presence of cavities allows more space for bulky intermediates and/or products and also provides room for molecules to drive consecutive reactions toward thermodynamic equilibrium. Channels, on the other hand, allow diffusion without trapping if their free diameters…
Mössbauer Study of Lanthanum–Strontium Ferromanganite Oxides
2004
The La0.88Sr0.2Mn(1−y)Fey0(3±δ, i (LSMF with y = 0, 0.2, 0.5, 0.8, 1) compounds are prospective cathode materials for advanced solid oxide fuel cells (SOFC) application operating at 700° C. Usual analysis methods like thermogravimetric analysis or redox titration enable to determine the average oxidation state of both manganese and iron cations. The comparative role of iron and manganese in B-site was evaluated by 57Fe Mossbauer spectroscopy. Spectra revealed that the complete substitution of iron for manganese induces the formation of Fe5+ for the compound with y = 1. However, no tetravalent iron cation was observed in air for the LSMF compounds with y = 0.2, 0.5 and 0.8. This means that o…
Untersuchungen von polymeren im massenspektrometer, 4. Abbaureaktionen von polybenzylen
1974
Die Abbaureaktionen von unsubstituierten Poly(1,4-phenylenmethylen)en (A) (Polybenzylen), Poly[(2,5-dimethyl-1,4-phenylen)methylen] [Poly(2,5-dimethylbenzyl)] (B), Poly[(2,3,5,6-tetramethyl-1,4-phenylen)methylen] [Poly(2,3,5,6-tetramethylbenzyl)] (C) und Poly(1,4-phenylenathyliden) [Poly(α-methylbenzyl)] (D) wurden durch direkte Pyrolyse im Massenspektrometer untersucht. Die Massenpyrogramme von unter verschiedenen Reaktionsbedingungen dargestellten Polybenzylen wurden verglichen, mit dem Ziel, direkt Informationen uber Strukturunterschiede wie Kettenverzweigung und unterschiedliche Verknupfung der Benzyleinheiten zu erhalten; hierbei konnten in einem Falle auf hohere Kettenverzweigung deut…