Search results for "Catalysis"

Cobalt−NHC Catalyzed C(sp2)−C(sp3) and C(sp2)−C(sp2) Kumada Cross‐Coupling of Aryl Tosylates with Alkyl and Aryl Grignard Reagents

2021

The first cobalt‐catalyzed cross‐coupling of aryl tosylates with alkyl and aryl Grignard reagents is reported. The catalytic system uses CoF3 and NHCs (NHC=N‐heterocyclic carbene) as ancillary ligands. The reaction proceeds via highly selective C−O bond functionalization, leading to the corresponding products in up to 98 % yield. The employment of alkyl Grignard reagents allows to achieve a rare C(sp2)−C(sp3) cross‐coupling of C−O electrophiles, circumventing isomerization and β‐hydride elimination problems. The use of aryl Grignards leads to the formation of biaryls. The C−O cross‐coupling sets the stage for a sequential cross‐coupling by exploiting the orthogonal selectivity of the cataly…

Molecular Basis of the Chemiluminescence Mechanism of Luminol

2019

Light emission from luminol is probably one of the most popular chemiluminescence reactions due to its use in forensic science, and has recently displayed promising applications for the treatment of cancer in deep tissues. The mechanism is, however, very complex and distinct possibilities have been proposed. By efficiently combining DFT and CASPT2 methodologies, the chemiluminescence mechanism has been studied in three steps: 1)luminol oxygenation to generate the chemiluminophore, 2)a chemiexcitation step, and 3)generation of the light emitter. The findings demonstrate that the luminol double-deprotonated dianion activates molecular oxygen, diazaquinone is not formed, and the chemiluminopho…

2-propanol formation by propene hydration: Catalytic and catalytic photo- assisted reaction using H3PW12O40 supported on TiO2 and SiO2.

2012

Comparison between catalytic and catalytic photo-assisted propene hydration by using supported polyoxometalate.

2012

A study on the catalytic perfomances of H3PW12O40 supported on TiO2 and SiO2 for propene hydration in the presence and in the absence of UV light

2012

Tuning Azoheteroarene Photoswitch Performance through Heteroaryl Design

2017

International audience; Photoswitchable compounds, which can be reversibly switched between two isomers by light, continue to attract significant attention for a wide array of applications. Azoheteroarenes represent a relatively new but understudied type of photoswitch, where one of the aryl rings from the conventional azobenzene class has been replaced with a five-membered heteroaromatic ring. Initial studies have suggested the azoheteroarenes – the arylazopyrazoles in particular – to have excellent photoswitching properties (quantitative switching and long Z isomer half-life). Here we present a systematic computational and experimental study to elucidate the origin of the long thermal hal…

Molecular orbital studies on the mechanism of catalytic isomerization of xylenes II. The photochemical process

1981

Abstract The feasibility of an intermediate step in the mechanism of photochemical isomerization of xylenes in acidic media is explored by using CNDO molecular orbital methods. Along the reaction path from 2,6-dimethylbenzenium ion to dimethylbicyclo[3.1.0]hexenyl cation, the energy surfaces for this intermediate step have been drawn both for the first singlet S1 and triplet T1 excited states. The energies of these excited states have been calculated by adding to the ground-state energy calculated by CNDO/2 method the excitation energy calculated by CNDO/S-CI method. An optimization of the saddle point energy is achieved by introducing the angle between methyl groups and the ring plane as a…

In situ polymerization of soil organic matter by oxidative biomimetic catalysis

2017

Abstract Background Agricultural practices that enhance organic matter content in soil can play a central role in sequestering soil organic carbon (SOC) and reducing greenhouse gases emissions. Methods We used a water-soluble iron-porphyrin to catalyze directly in situ oxidative polymerization of soil organic matter in the presence of H2O2 oxidant, with the aim to enhance OC stabilization, and, consequently, reduce CO2 emissions from soil. The occurred SOC stabilization was assessed by monitoring soil aggregate stability, OC distribution in water-soluble aggregates, soil respiration, and extraction yields of humic and fulvic acids. Results Soil treatment with H2O2 and iron-porphyrin increas…

Photocatalytic CO 2 Valorization by Using Ti O2 , ZrO2 and Graphitic Based Semiconductors

2018

In this century, a broad scientific interest has been devoted to fulfill sustainable industrial processes and climatic change remediation. In this prospective, various green technologies have been studied to valorize CO 2• The aim of this research is the CO 2 reduction in presence of water by using the photocatalytic technology with nanomaterials as the photocatalysts. The present work overviews the main outcomes obtained by using graphitic and oxide based photocatalysts both in gas/solid and liquid/solid batch reactors under simulated solar light. In all gas/solid regime tests the major products detected were methane, carbon monoxide, and acetaldehyde.

Photoreduction of carbon dioxide to formic acid in aqueous suspension: a comparison between phthalocyanine/TiO2 and porphyrin/TiO2 catalysed processes

2014

Composite materials prepared by loading polycrystalline TiO2 powders with lipophilic highly branched Cu(II)- and metal-free phthalocyanines or porphyrins, which have been used in the past as photocatalysts for photodegradative processes, have been successfully tested for the efficient photoreduction of carbon dioxide in aqueous suspension affording significant amounts of formic acid. The results indicated that the presence of the sensitizers is beneficial for the photoactivity, confirming the important role of Cu(II) co-ordinated in the middle of the macrocycles. A comparison between Cu(II) phthalocyanines and Cu(II) porphyrins indicated that the Cu(II)- phthalocyanine sensitizer was more e…