Characterization Study of CO2, CH4, and CO2/CH4 Hydroquinone Clathrates Formed by Gas–Solid Reaction

Hydroquinone (HQ) is known to form organic clathrates with some gaseous species such as CO2 and CH4. This work presents spectroscopic data, surface and internal morphologies, gas storage capacities, guest release temperatures, and structural transition temperatures for HQ clathrates obtained from pure CO2, pure CH4, and an equimolar CO2/CH4 mixture. All analyses are performed on clathrates formed by direct gas–solid reaction after 1 month’s reaction at ambient temperature conditions and under a pressure of 3.0 MPa. A collection of spectroscopic data (Raman, FT-IR, and 13C NMR) is presented, and the results confirm total conversion of the native HQ (α-HQ) into HQ clathrates (β-HQ) at the end of the reaction. Optical microscopy and SEM analyses reveal morphology changes after the enclathration reaction, such as the presence of surface asperities. Gas porosimetry measurements show that HQ clathrates and native HQ are neither micro- nor mesoporous materials. However, as highlighted by TEM analyses and X-ray tomography, α- and β-HQ contain unsuspected macroscopic voids and channels, which create a macroporosity inside the crystals that decreases due to the enclathration reaction. TGA and in situ Raman spectroscopy give the guest release temperatures as well as the structural transition temperatures from β-HQ to α-HQ. The gas storage capacity of the clathrates is also quantified by means of different types of gravimetric analyses (mass balance and TGA). After having been formed under pressure, the characterized clathrates exhibit exceptional metastability: the gases remain in the clathrate structure at ambient conditions over time scales of more than 1 month. Consequently, HQ gas clathrates display very interesting properties for gas storage and sequestration applications

Short-Lived Orthobenzyne Complexes with Early Transition Metals of Group IV. First Direct Characterization and Electronic Cartography by Coupling FVT/UV-PES with Calculations

International audienceShort‐lived eta2‐benzyne metallocene complexes [Cp2M(eta2‐c‐C6H4)] with Gp IV metals are important intermediates in organic chemistry, their olefin insertion products being building block for aromatic and heterocyclic compounds. For the first time, an electronic cartography of these short‐lived species has been obtained through the determination of their ionization potentials. They have been directly characterized in gas phase by UV‐Photoelectron Spectroscopy by monitoring in‐situ the thermal beta‐H abstraction of benzene from Cp2MPh2. The metal impacts more strongly the energetic position of the sigmaMC orbitals than the piCCbenzyne orbital (HOMO). This study has been supported by DFT calculations and by NBO, AIM, ELF, EDA analyses. Electronic structure of the transient Cp2Ti(eta2‐c‐C6H4) complex is peculiar and slightly differs from that of their zirconium and hafnium analogous. It results in a combination between metallacycle and pi‐complex, whereas with Hf and Zr the metallacycle structure appears to be more representative

Stereocontrolled alpha-alkylation of oxime ether derived from terpene: efficient synthesis of new chiral gamma - and delta-amino alcohols

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Soil-Gas Concentrations and Flux Monitoring at the Lacq-Rousse CO2-Geological Storage Pilot Site (French Pyrenean Foreland): From Pre-Injection to Post-Injection

International audienceSoil-gas concentrations and flux were measured during 20 separate measurement campaigns at the TOTAL Lacq-Rousse carbon capture and storage (CCS) pilot site, southern France, where 51,000 tons of CO2 were injected in a depleted natural gas field. Baseline data (September 2008 to December 2009) are compared to monitoring data from the injection (March 2010 to March 2013) and post-injection (February 2014 to December 2015) periods. CO2 soil-gas concentrations varied from atmospheric concentrations to more than 16% vol. with 1.4% as median value. Summer data showed high CO2 concentrations in the soil that remained quite high during winter. Median CO2 flux at the soil/atmosphere interface was close to 4.4 cm(3).min(-1.)m(-2). Carbon-isotope ratios measured on CO2 in soil gas had a mean value of -23.5 +/- 3.1 parts per thousand, some deviation being due to atmospheric CO2. Comparison between different gas species and the influence of temperature, pressure and soil-water content suggest that gases in near-surface environments are produced locally and naturally, and are unrelated to CO2 ascending from the storage reservoir. Monitoring of CO2 injection and the use of threshold levels is discussed as part of a practical approach considering specific regulations for the Lacq-Rousse CCS pilot experiment and constraints for the site operator

Chiral phosphinoazomethinylate salts as new ‘one-step available’ ligands for copper-catalyzed asymmetric conjugate addition

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Mesoscale distribution of zooplankton biomass in the northeast Atlantic Ocean determined with an Optical Plankton Counter: Relationships with environmental structures

We examined the mesoscale distribution of zooplankton populations using a continuous recording system: the optical plankton counter (OPC). Data were collected in the mid-latitude northeast Atlantic inter-gyre region in April and September 2001 during the POMME 2 and POMME 3 cruises. This sector of the North Atlantic system is characterized by subduction phenomena and mesoscale eddies. Estimated mean biomass was 2.88 DW g m(-2) in April and 1.64DW g m(-2) in September with populations dominated by small copepods of the genera, Clausocalanus, Paracalanus and Oithona. Day-night changes in vertical distribution appeared to be seasonally variable. During April, absolute concentrations within the upper layer above 50 m were higher at night. During September, vertical profiles of relative biomass were quite similar for day and night. Highest depth-integrated biomasses were located mainly on the periphery of anticyclonic eddies, with maxima related to the increase in depth range of vertical distribution. This pattern suggested that maximum biomass was associated with the most dynamic parts of the frontal features. Other zones of high zooplankton biomass were associated with the centers of cyclonic eddies and high fluorescence values. Using a 3D view, we found that zooplankton distribution showed a more complex pattern than in a 2D view with variable vertical distribution. Hence, proper description of the distribution of zooplankton underlines the need to describe this submesoscale with an order of magnitude around 10 nautical miles. (C) 2009 Elsevier Ltd. All rights reserved

Experimental and Theoretical Studies on the Mechanism of the C-S Bond Activation of PdII Thiolate/Thioether Complexes

International audienceTwo equivalents of L (L = 4-methylthio-2-thioxo-1,3-dithiole-5-thiolate or Medmit) react with cis-Pd(PR3)2Cl2 (R = Ph and Et) to afford Pd(PR3)(η1-L)(η2-L) (R = Et: 1 ; R = Ph: 2) complexes, which have been characterized by X-ray crystallography. These compounds are dynamic in solution due to an exchange of the thiomethyl groups on palladium. Variable-temperature 1H NMR spectroscopy reveals a low coalescence temperature (173 K). Treatment of Pd(diphos)Cl2 (diphos = dppe or dppm) with 2 equiv of L affords thiolato complexes Pd(dppe)(η1-L)2 (3) and Pd(dppm)(η1-L)2 (4). Whereas 3 is rigid in solution with firm η2-coordination of dppe and η1-coordination of the thiolate, two linkage isomers Pd(η2-dppm)(η1-L)2 and Pd(η1-dppm)(η1-L)(η2-L) coexist in a solution of 4. L coordinated on PdII undergoes a S-demethylation reaction leading to dithiolene complexes and MeL. This transformation requires high temperature, and its efficiency depends on the nature of the phosphines as well as the nature of the metal (Pd vs Pt). DFT calculations reveal that the most likely mechanism depends on the lability of phosphines. Starting from M(PR3)2(η1-L)2 (M= Pd and Pt; R = Ph and Et), the favored sequence implies decoordination of one triethyl phosphine (M(PEt3)(η1-L)(η2-L)2 as intermediate) or two triphenylphosphines (Pd(η2-L)2 as intermediate) followed by oxidative addition and reductive elimination (OA/RE) reactions. In the case of PEt3, this OA/RE sequence can also compete with an intramolecular nucleophilic addition (AN), which can be described as an attack of a thiolate sulfur atom on a CH3+ carbocation. An intramolecular SN2 process was found to be the most feasible, starting from M(dppe)(η1-L)2 (M= Pd and Pt), with the nucleophile approaching the thiomethyl group at an angle of 180° with respect to the CCH3–S bond. The influence of the coligand has also been studied experimentally. Structurally characterized disulfide L–L dimer has been isolated upon reaction of 2 equiv of L with MCl2 (M = Pd and Pt)

Allyl Complexes of Tungsten from the Rearrangement of Transient Cyclopropyl Precursors

International audienceThis article explores the contrasting reactivity of cyclopropyl complexes of early transition metals. [Cp*W(NO)(CH2R)(c‐C3H5)] (R = SiMe3, Ph, t‐Bu) generated in THF solution from [Cp*W(NO)(CH2R)Cl] and [Mg(c‐C3H5)2(dioxane)x] readily rearrange to η3‐allyl derivatives [Cp*W(NO)(CH2R)(η3‐C3H5)] by an intramolecular ring opening reaction. Both direct and catalyzed pathways are revealed by kinetic studies. Computational modeling indicates the ring opening reaction is preferred on thermodynamic grounds for tungsten whereas kinetic products arising from β‐H abstraction reactions of cyclopropane are observed for related zirconium and niobium complexes reported previously. The energetic accessibility and the nature of the LUMO in the tungsten complexes promote distal CC bond cleavage in the cyclopropyl ring

Desulfovibrio marrakechensis sp nov., a 1,4-tyrosol-oxidizing, sulfate-reducing bacterium isolated from olive mill wastewater

A novel mesophilic sulfate-reducing bacterium, EMSSDQ(4)(T), was isolated from olive mill wastewater in the semi-arid region of Morocco (Marrakech). Cells were Gram-negative, catalase-positive, straight rods that were non-motile and non-spore-forming and contained cytochrome c(3) and desulfoviridin. The DNA G + C content was 65.1 mol%. Phylogenetic analysis based on 16S rRNA gene sequences revealed that the isolate was a member of the genus Desulfovibrio with Desulfovibrio carbinoliphilus D41(T), Desulfovibrio alcoholivorans SPSNT, Desulfovibrio fructosivorans JJ(T) and Desulfovibrio carbinolicus EDK82(T) as the most closely related strains with validly published names. In addition to the classical substrates used by Desulfovibrio species, the isolate oxidized 1,4-tyrosol, one of the most abundant phenolic compounds occurring in olive mill wastewater, to 4-hydroxyphenylacetate without ring cleavage. D. alcoholivorans SPSNT was also found to carry out this reaction. Under air, strain EMSSDQ(4)(T) exhibited limited growth on lactate and yeast extract in the absence of sulfate. On the basis of genotypic and phenotypic characteristics, it is proposed that the isolate represents a novel species, Desulfovibrio marrakechensis sp. nov. The type strain is EMSSDQ(4)(T) (=DSM 19337(T) =ATCC BAA-1562(T))

(Cyclopentadienyl)iron(II) complexes of N-heterocyclic carbenes bearing a malonate or imidate backbone: Synthesis, structure, and catalytic potential in hydrosilylation

0276-7333International audienceThe backbone-functionalized anionic carbenes maloNHC (1R; malonate backbone) and imidNHC (2; imidate backbone) were generated in situ from their respective zwitterionic precursors and treated with FeCp(CO)2I to afford the zwitterionic complexes {FeCp(CO)2(1R)} (3R; 59-84% yield), and {FeCp(CO)2(2)} (4; 77% yield), respectively. Methylation of the malonate complex 3Me takes place at one of the backbone oxygen atoms to give the cationic adduct [FeCp(CO)2(1MeMe)](OTf) ([5Me](OTf); 96% yield), whereas methylation of 4 takes place at the imidate nitrogen atom to produce the cationic adduct [FeCp(CO)2(2Me)](OTf) ([6Me](OTf); 84% yield). All of the complexes were characterized by NMR and IR in solution, while X-ray structure analyses were carried out for 3Me, 4, and [6Me](OTf). In addition, a detailed experimental and theoretical investigation of the electron density within the archetypal zwitterionic complex 3Me was carried out. The observation of short intramolecular contacts between Cipso or Cortho of the mesityl groups of the carbene and the proximal carbonyl groups is rationalized in terms of a noncovalent "through space" π-π* interaction involving a two-electron delocalization of the occupied π(Cipso=Cortho) molecular orbital (MO) of the aryl ring into one vacant π*(C=O) MO of the carbonyl ligand. A theoretical analysis carried out on dissymmetrical model complexes reveals that the magnitude of such an interaction is correlated with the donor properties of aryl group substituents. A catalyst screening of the above complexes in the hydrosilylation of benzaldehyde under visible light irradiation revealed a dramatic effect of the electronic donor properties of these carbenes on the performances of their complexes, with the more nucleophilic carbene 1tBu- in the zwitterionic species 3tBu appearing as the most efficient. This complex shows good efficiency and excellent chemoselectivity in the hydrosilylation of various aldehydes bearing reactive functional groups. It is also moderately active in the hydrosilylation of a few ketone substrates and exhibits very good performance in the hydrosilylation of representative aldimines and ketimines