79 research outputs found
Formation of Alkanes by Aerobic CarbonâCarbon Bond Coupling Reactions Catalyzed by a Phosphovanadomolybdic Acid
The valorization of alkanes is possible via carbonâcarbon coupling reactions. A series of dialkyl cobalt complexes [(RCH_2)_2Co^(III)(bpy)_2]ClO_4 (R = H, Me, Et, and Ph) were reacted with the H_5PV_2Mo_(10)O_(40) polyoxometalate as a catalyst, leading to a selective oxidative carbonâcarbon bond coupling reaction. The reaction is initiated by electron transfer from [(RCH_2)_2Co^(III)(bpy)_2]^+ to H_5PV^V_2Mo_(10)O_(40) to yield an intermediate [(RCH_2)_2Co^(IV)(bpy)_2]^(2+)âH_5PV^(IV)V^VMo_(10)O_(40), as identified by a combination of EPR and X-ray photoelectron spectroscopy experiments. The reaction is catalytic with O_2 as terminal oxidant representing an aerobic CâC bond coupling reaction
Improving Fatigue Resistance of Dihydropyrene by Encapsulation within a Coordination Cage
Photochromic molecules undergo reversible isomerization upon irradiation with light at different wavelengths, a process that can alter their physical and chemical properties. For instance, dihydropyrene (DHP) is a deep-colored compound that isomerizes to light-brown cyclophanediene (CPD) upon irradiation with visible light. CPD can then isomerize back to DHP upon irradiation with UV light or thermally in the dark. Conversion between DHP and CPD is thought to proceed via a biradical intermediate; bimolecular events involving this unstable intermediate thus result in rapid decomposition and poor cycling performance. Here, we show that the reversible isomerization of DHP can be stabilized upon confinement within a (PdIIL4)-L-6 coordination cage. By protecting this reactive intermediate using the cage, each isomerization reaction proceeds to higher yield, which significantly decreases the fatigue experienced by the system upon repeated photocycling. Although molecular confinement is known to help stabilize reactive species, this effect is not typically employed to protect reactive intermediates and thus improve reaction yields. We envisage that performing reactions under confinement will not only improve the cyclic performance of photochromic molecules, but may also increase the amount of product obtainable from traditionally low-yielding organic reactions
Polymorphism of L-tryptophan
A new polymorph of Lâtryptophan has been prepared by crystallization from the gas phase, with structure determination carried out directly from powder XRD data augmented by periodic DFTâD calculations. The new polymorph (denoted ÎČ) and the previously reported polymorph (denoted α) are both based on alternating hydrophilic and hydrophobic layers, but with substantially different hydrogenâbonding arrangements. The ÎČ polymorph exhibits the energetically favourable L2âL2 hydrogenâbonding arrangement, which is unprecedented for amino acids with aromatic sideâchains; the specific molecular conformations adopted in the ÎČ polymorph facilitate this hydrogenâbonding scheme while avoiding steric conflict of the sideâchains
Nuevos datos acerca de los repertorios teatrales en el primer catålogo de «El peregrino en su patria»
En este artĂculo se muestra cĂłmo los tĂtulos que contienen los repertorios de los autores de comedias presentes en El peregrino en su patria de 1604 estĂĄn dispuestos segĂșn un orden cronolĂłgico, aunque con algunos matices y no pocas excepciones. AdemĂĄs, se amplĂan los repertorios descubiertos por Thornton Wilder y se afina la fecha de composiciĂłn de varias obras, prestando especial atenciĂłn a textos que se han perdido, como La perdiciĂłn de España, La gobernadora, La gran pintora, La bella gitana o La toma de Ălora. Finalmente, el presente artĂculo pretende mostrar de un modo prĂĄctico cĂłmo una base de datos digital como el Diccionario biogrĂĄfico de actores del teatro clĂĄsico español (DICAT) puede resultar de gran ayuda a la hora de resolver algunos de los problemas clĂĄsicos de la filologĂa en general y del teatro del Siglo de Oro en particular.This paper shows that the plays contained in the repertoire of the autores de comedias which appear in El peregrino en su patria (1604) are organised chronologically, although there are some nuances and exceptions. The article also expands the repertoire discovered by Thornton Wilder and sets the date of composition for some plays, paying special attention to lost texts such as La perdiciĂłn de España, La gobernadora, La gran pintora, La bella gitana or La toma de Ălora. Finally, this paper attempts to show in a practical way that a database such as the Diccionario biogrĂĄfico de actores del teatro clĂĄsico español (DICAT) can be extremely helpful when it comes to dealing with some of the philology's classical problems in general and those of the theatre of the Golden Age in particular
Crystal structure of a new polymorph of (2S,3S)-2-amino-3-methylpentanoic acid
A new polymorph of (2S,3S)-2-amino-3-methylpentanoic acid, l-isoleucine C6H13NO2, crystallizes in the monoclinic space group P21 with four independent molecules in the asymmetric unit. The molecules are zwitterions. In the crystal, NâH...O hydrogen bonds link two pairs of independent molecules and their symmetry-related counterparts to form two types of layers stacked in an anti-parallel manner parallel to (001). The hydrophobic aliphatic isopropyl groups protrude from these layers
Formal oxidative addition of a C-H bond by a 16e iridium(I) complex involves metal-ligand cooperativity
The first example of oxidative addition of a CâH bond to a square planar d8-Iridium complex, without any external additive, such as an acid, is described. Our mechanistic investigations show that metalâligand cooperation through aromatizationâdearomatization of the lutidine backbone is involved in this process, and that the actual CâH activation step occurs through an Ir(III) intermediate
Controlled selectivity through reversible inhibition of the catalyst: Stereodivergent semihydrogenation of alkynes
Catalytic semihydrogenation of internal alkynes using H2 is an attractive atom-economical route to various alkenes, and its stereocontrol has received widespread attention, both in homogeneous and heterogeneous catalysis. Herein, a novel strategy is introduced, whereby a poisoning catalytic thiol is employed as a reversible inhibitor of a ruthenium catalyst, resulting in the first controllable H2-based semihydrogenation of internal alkynes. Both (E)- and (Z)-alkenes were obtained efficiently and highly-selectively, under very mild conditions, using a single homogenous acridine-based ruthenium catalyst. Mechanistic studies indicate that the (Z)-alkene is the reaction intermediate leading to the (E)-alkene, and that addition of a catalytic amount of bidentate thiol impedes the Z-E isomerization step by forming stable ruthenium thiol(ate) complexes, while still allowing the main hydrogenation reaction to proceed. Thus, the absence or presence of catalytic thiol controls the stereoselectivity of this alkyne semihydrogenation, affording either the (E)-isomer as the final product, or halting the reaction at the (Z)-intermediate. The developed system, which is also applied to the controllable isomerization of a terminal alkene, demonstrates how selective metal catalysis can be achieved by reversible inhibition of the catalyst with a simple auxiliary additive
Formamides as Isocyanate Surrogates: A Mechanistically Driven Approach to the Development of Atom-Efficient, Selective Catalytic Syntheses of Ureas, Carbamates, and Heterocycles
International audienceDespite the hazardous nature of isocyanates, they remain key building blocks in bulk and fine chemical synthesis. By surrogating them with less potent and readily available formamide precursors, we herein demonstrate an alternative, mechanistic approach to selectively access a broad range of ureas, carbamates and heterocycles via a ruthenium-based pincer complex catalyzed acceptorless dehydrogenative coupling reactions. The design of these highly atom-efficient procedures was driven by the identification and characterization of the relevant organometallic complexes, uniquely exhibiting the trapping of an isocyanate intermediate. DFT calculations further contributed to shed light on the remarkably orchestrated chain of catalytic events, involving metal-ligand cooperation
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