Search results for "Lewis"

The Taming of Redox‐Labile Phosphidotitanocene Cations

2019

International audience; Tame d0 phosphidotitanocene cations stabilized with a pendant tertiary phosphane arm are reported. These compounds were obtained by one-electron oxidation of d1 precursors with [Cp2Fe][BPh4]. The electronic structure of these compounds was studied experimentally (EPR, UV/Vis, and NMR spectroscopy, X-ray diffraction analysis) and through DFT calculations. The theoretical analysis of the bonding situation by using the electron localization function (ELF) shows the presence of π-interactions between the phosphido ligand and Ti in the d0 complexes, whereas dπ–pπ repulsion prevents such interactions in the d1 complexes. In addition, CH–π interactions were observed in seve…

9,10-Phenanthrenedione as Visible-Light Photoredox Catalyst: A Green Methodology for the Functionalization of 3,4-Dihydro-1,4-Benzoxazin-2- Ones thro…

2018

A visible-light photoredox functionalization of 3,4-dihydro-1,4-benzoxazin-2-ones through a Friedel-Crafts reaction with indoles using an inexpensive organophotoredox catalyst is described. The reaction uses a dual catalytic system that is formed by a photocatalyst simple and cheap, 9,10-phenanthrenedione, and a Lewis acid, Zn(OTf)2. 5W white LEDs are used as visible-light source and oxygen from air as a terminal oxidant, obtaining the corresponding products with good yields. The reaction can be extended to other electron-rich arenes. Our methodology represents one of the most valuable and sustainable approach for the functionalization of 3,4-dihydro-1,4-benzoxazin-2-ones, as compared to th…

Dual role of silver in a fluorogenic N-squaraine probe based on Ag(i)–π interactions

2021

In the presence of Ag(I), the monoanion of cyano-N-squaraine (I) generates an intense fluorescence turn-on response. Experimental evidence and DFT calculations reveal a sequence of deprotonation-coordination events in which the Ag(I) ions play a dual role as a Lewis acid and coordinating metal. The observed effect is highly selective for Ag(I) compared to other metals.

Reversible O–H bond activation by an intramolecular frustrated Lewis pair

2019

The interactions of the O-H bonds in alcohols, water and phenol with dimethylxanthene-derived frustrated Lewis pairs (FLPs) have been probed. Within the constraints of this backbone framework, the preference for adduct formation or O-H bond cleavage to give the corresponding zwitterion is largely determined by pKa considerations. In the case of the PPh2/B(C6F5)2 system and p-tBuC6H4OH, an equilibrium is established between the two isomeric forms which allows the thermodynamic parameters associated with zwitterion formation via O-H bond cleavage to be probed.

Lewis Base Catalyzed Intramolecular Reduction of Salicylaldehydes by Pinacol-Derived Chlorohydrosilane

2018

A robust viologen and Mn-based porous coordination polymer with two types of Lewis acid sites providing high affinity for H 2 O, CO 2 and NH 3

2017

A novel porous coordination polymer [Mn(pc3)(H2O)2]·xH2O (3 < x < 4) is synthesized in water at pH = 7 using the anionic viologen-carboxylate ligand 4,4′-bipyridinium,1,1′-bis-(2,4-dicarboxyphenyl) (pc32−). Dehydration of the material results in the formation of open pores containing two types of accessible Lewis acid sites: exposed Mn2+ cations and N+ atoms of viologen units. Due to this property the PCP shows high affinity and capacity in the adsorption of H2O, CO2 and NH3. Despite the presence of strong adsorption sites this material is stable in liquid water and in gaseous NH3.

Enantioselective synthesis of chiral oxazolines from unactivated ketones and isocyanoacetate esters by synergistic silver/organocatalysis

2018

[EN] A multicatalytic approach that combines a bifunctional Brønsted base¿squaramide organocatalyst and Ag+ as Lewis acid has been applied in the reaction of unactivated ketones with tert-butyl isocyanoacetate to give chiral oxazolines bearing a quaternary stereocenter. The formal [3+2] cycloaddition provided high yields of the corresponding cis-oxazolines with good diastereoselectivity and excellent enantioselectivity, being applied to aryl¿alkyl and alkyl¿alkyl ketones.

Comparative hydroamination of aniline and substituted anilines with styrene on different zeolites, triflate based catalysts and their physical mixtur…

2014

Abstract Catalytic performances of different zeolites (Beta and mordenites), scandium triflate based catalysts, mesoporous UVM-7 encapsulated scandium triflate and physical mixtures prepared under ultrasound irradiation were evaluated in the hydroamination of aniline and substituted anilines with styrene. The performances of these catalysts were controlled by the type of acidity and strength. Thus, the conversion was mainly controlled by the strength of the acid sites and their accessibility, while the selectivity appeared to be controlled by the Lewis/Bronsted type of acidity. Lewis acid catalysts directed the reactions mainly to the formation of the Markovnikov adducts while Bronsted acid…

A Ferrocenyl Amino Substituted Stannylene as an Intramolecular Fe→Sn Lewis Adduct

2018

Subduction or sagduction? Ambiguity in constraining the origin of ultramafic–mafic bodies in the Archean crust of NW Scotland

2016

Abstract The Lewisian Complex of NW Scotland is a fragment of the North Atlantic Craton. It comprises mostly Archean tonalite–trondhjemite–granodiorite (TTG) orthogneisses that were variably metamorphosed and reworked in the late Neoarchean to Paleoproterozoic. Within the granulite facies central region of the mainland Lewisian Complex, discontinuous belts composed of ultramafic–mafic rocks and structurally overlying garnet–biotite gneiss (brown gneiss) are spatially associated with steeply-inclined amphibolite facies shear zones that have been interpreted as terrane boundaries. Interpretation of the primary chemical composition of these rocks is complicated by partial melting and melt loss…