The Reactivity Of singlet carbenes. An ab initio study

The energy barriers for the addition to ethylene of a series of carbenes have been calculated at an ab initio level. using the STO-3G and 3-21G basis sets. It is shown that the usual extrapolation of experiment results, which predicts that the reactivity of carbenes decreases when increasing its nucleophilic character, is not valid.     

Sur le problème de Plateau pour un quadrilatère variable qui peut acquérir un point double

Résumé Soit Γ un quadrilatère variable, dont deux c?tés opposés A₂A₃, A₁A₄ sont dans les plans x₃=c, x₃=−c. Quand c tend vers0, Γ tend vers un quadrilatèreΓ ⁰ présentant un point double, A⁰. Le travail étudie la représentation conforme sur le demi-plan R(ix)<0 (ou sur le cercle - unité) de la surface minimale ∑ passant par Γ. Il montre (§ I) que si les affixes x de A₁, A₂, A₄ sont 0, 1, ∞, l'affixe de A₃ sera ɛ⁻², où ɛ tend vers 0 avec c. Il étudie (§ II) l'allure pour ɛ tendant vers 0 des intégrales canoniques de l'équation linéaire du problème. La forme de la relation entre ɛ et c est indiquée au n^o 19; on montre que dans la région de striction ɛ |x| reste borné et que la surface ∑ y est assimilable à une surface minimale simple: la surface de vis à filet carré. La représentation conforme de l'une des deux régions de ∑ qui tendent à se séparer l'une de l'autre tend à envahir tout le demi-plan (ou tout le cercle-unité). Les représentations conformes de ∑ pour c>0 et c<0 ne sont pas analytiquement distinctes (n⁰ 20). A titre d'exemple, on étudie (n⁰ 21) le cas où ∑ possède un axe de symétrie. A M. Enrico Bompiani pour son Jubilé scientifique     

Pulsed-field gradient nuclear magnetic resonance study of transport properties of fluid catalytic cracking catalysts

Pulsed-field gradient nuclear magnetic resonance (PFG NMR) has been applied to study molecular diffusion in industrial fluid catalytic cracking (FCC) catalysts and in USY zeolite for a broad range of molecular displacements and temperatures. The results of this study have been used to elucidate the relevance of molecular transport on various displacements for the rate of molecular exchange between catalyst particles and their surroundings. It turned out that this rate, which may determine the overall rate and selectivity of FCC process, is primarily related to the diffusion mode associated with displacements larger than the size of zeolite crystals located in the particles but smaller than the size of the particles. This conclusion has been confirmed by comparative studies of the catalytic performance of different FCC catalysts.     

2-Methoxy-6-oxo-1,4,5,6-tetrahydropyridine-3-carbonitriles: versatile starting materials for the synthesis of libraries with diverse heterocyclic scaffolds

Heterocyclic demonstration libraries for agrochemical screening were prepared from the common intermediates 2-methoxy-6-oxo-1,4,5,6-tetrahydropyridine-3-carbonitriles (1), using standard solution-phase techniques. A total of 18 screening libraries were prepared in good to excellent yields. Several members of these libraries were active in the first level of agrochemical screening, especially in the fungicide screen.     

Isolation and structural elucidation of a novel rotenoid from the seeds of Clitoria fairchildiana

The seeds of Clitoria fairchildiana provided a new rotenoid, 6-hydroxy-2,3,9-trimethoxy-[1]benzopyrano[3,4-b][1]benzopyran-12(6H)-one. The structural elucidation was performed using detailed analyses of H- and 13C-NMR spectra including 2DNMR spectroscopic techniques (1H-13CHETCOR) and by comparison with spectrometric data from the literature. The anti-inflammatory activity was investigated using a capillary permeability assay.     

Mechanism and kinetics of the catalytic CO-H2 reaction: An approach by chemical transients and surface relaxation spectroscopy

The aim of this paper is to demonstrate the importance of providing time-resolved information in catalysis research. Two truly in situ methods will be presented and compared for their merits and drawbacks: chemical transient kinetics (CTK) and pulsed field desorption mass spectrometry (PFDMS). The presentation will be given by way of example choosing the syngas (CO/H2) reaction over cobalt-based catalysts as a catalytic process. Despite numerous efforts in the past, the mechanism of this reaction is still under debate. In CTK the reaction is studied on a metal-supported catalyst under flow conditions in a pressure range extending from atmospheric pressure down to 100 Pa. Sudden changes in the partial pressures of the reactants then allow following the relaxation to either steady-state conditions ("transients") or cleanoff ("back transients"). In PFDMS short field pulses of several volts per nanometer are applied to a model catalyst which resembles a single metal particle grain (a "tip"). These pulses intervene during the ongoing reaction under flow conditions at pressures ranging from 10(-1) to 10(-5) Pa and cause field desorption of adsorbed species. This method is particularly suited to detect reaction intermediates in a time-dependent manner since the repetition frequency of the pulses can be systematically varied. It is shown that both methods lead to complementary results. While CTK allows conclusions on the mechanism of CO hydrogenation by following the time-dependent formation of hydrocarbon species, PFDMS provides insight into the initial steps leading to adsorbed CxHy species. A quantitative assessment of the CTK data allows the demonstration that the catalyst under working conditions is in an oxidized rather than metallic state. The initial steps to oxidation are also traced by PFDMS. Most importantly, however, CTK results allow formulation of a reaction mechanism that is common for both hydrocarbon and oxygenate formation and is based on the occurrence of a formate-type species as the most abundant surface intermediate.     

Self-assembled networks of ribbons in molecular hydrogels of cationic deoxycholic acid analogues

Aqueous gels derived from three cationic 24-nor 3,12-dihydroxy cholane (DC) derivatives with N-methyl-2-pyrrolidinone (NMP), N-methylmorpholine (NMM), and 1,4-diazabicyclo[2.2.2]octane (DABCO) at the side chain positions have been exhaustively characterized by small-angle neutron-scattering experiments. Although the molecular structures differ slightly by the heterocycle grafted to the steroid core, the derived gels exhibit a range of structural behaviors at the nanoscale that depart from those observed with simple deoxycholate systems. The NMM-DC aggregates are ribbons with a bimolecular thickness of t = 37 A and an anisotropy of the section b/a approximately 0.1. DABCO-DC exhibits a remarkable transition from ribbons (t = 29.5 A, b/a = 0.18) to thicker cylindrical fibers (R approximately 59 A), involving four original ribbons, upon a concentration increase. The NMP-DC system forms thick cylindrical fibers (R approximately 68 A) with steroid molecules organized in a specific morphology. Bilayered or interdigited structures are formed and favored by the presence of multiple polar interaction centers in the DC molecules. Secondary aggregation mechanisms are invoked in the formation of bundles having a lower cross-sectional anisotropic symmetry and exhibiting Bragg peaks corresponding to molecular length periodicities. The relations between the structural information and the rheological properties are discussed.     

Elysiapyrones from Elysia diomedea. Do such metabolites evidence an enzymatically assisted electrocyclization cascade for the biosynthesis of their bicyclo[4.2.0]octane core?

[structure: see text] Biogenetically interesting polypropionate-derived metabolites 1 and 2, featuring an unprecedented skeleton, have been isolated from the sea slug Elysia diomedea. Their enantiomeric character indicates that the current spontaneous electrocyclization cascade biogenetic hypothesis for the bicyclo[4.2.0]octane core must be enzymatically aided. These compounds are isomeric with the 15-nor-9,10-deoxytridachione/15-norphotodeoxytridachione pair of metabolites and encourage speculation about their biosynthetic relationship.     

Gold cluster carbonyls: vibrational spectroscopy of the anions and the effects of cluster size, charge, and coverage on the CO stretching frequency

We report the vibrational spectra of the carbonyl complexes of anionic gold clusters in the range of the CO stretching frequency as measured in the gas phase using IR multiple photon dissociation spectroscopy. The investigated complexes contain between 3 and 14 Au atoms and up to 7 CO ligands. Special attention is given to the complexes that exhibit saturation CO coverage as well as to the monocarbonyl species. In conjunction with data from the corresponding cationic complexes we quantify how the CO stretching frequency varies with the charge state of the gold cluster. Our results provide a size- and charge-dependent basis to interpret values of the CO stretching frequency measured for CO on deposited gold clusters in terms of the charge states of the clusters.