Search results for "ASTER"

Ligand dynamics of tert-butyl isocyanide oxido complexes of molybdenum(IV).

2014

The six-coordinate molybdenum(IV) oxido isocyanide complex 1 [Δ,Λ-OC-6-2-3-[MoO(N(p)∩N(i))2(CN(t)Bu)]; N(p)∩N(i) = 4-tert-butylphenyl(pyrrolato-2-ylmethylene)amine] is obtained in diastereomerically pure form in the solid state, as revealed by single-crystal X-ray diffraction. In solution, this stereoisomer equilibrates with the Δ,Λ-OC-6-2-4 diastereomer 2 at ambient temperature. The stereochemistry of both isomers has been elucidated by NMR, IR, and UV/vis spectroscopy in combination with density functional theory (DFT)/polarizable continuum model and time-dependent DFT calculations. The isomerization 1 → 2 is suggested to proceed via a dissociative trigonal twist with dissociation of the …

Theoretical study of isomerism in phenoxyimine-based precursors of coordinative olefin polymerization catalysts

2010

Precursors of post-metallocene olefin polymerization catalysts, unlike their predecessors, are usually octahedral transition metal complexes with multidentate ligands. Such ligands may wrap around the central atom in many ways, thus yielding several isomeric species. For a wide range of phenoxyimine (FI) ligands with different substituents, all the theoretically predicted diastereomers of group 4 and 5 complexes are available synthetically. However, only one of the isomers is usually preferred, and this is determined by the nature of the substituents in the FI ligand. The origin and mechanism of such preference has not been completely elucidated. We attempted to describe it quantitatively o…

Synthesis, Coordination to Rh(I), and Hydroformylation Catalysis of New β-Aminophosphines Bearing a Dangling Nitrogen Group:  An Unusual Inversion of…

2002

Variants of the beta-aminophosphine L(1) [Ph(2)PCH(2)CH(Ph)NHPh] containing additional nitrogen donor functions have been prepared. These functions are branched off the C atom adjacent to the P atom, or the P atom itself. Ligand [Ph(2)PCH(o-C(6)H(4)NMe(2))CH(Ph)NHPh] has been obtained as a mixture of two diastereomers L(3A) and L(3B) by lithiation of L(2) [Ph(2)PCH(2)(o-C(6)H(4)NMe(2))] with n-BuLi followed by PhCH=NPh addition and hydrolysis. The diastereomers have been separated by fractional crystallization from ethanol. Ligand Et(2)NCH(2)P(Ph)CH(2)CH(Ph)NHPh has been obtained as a mixture of two diastereomers L(5A) and L(5B)(starting with P-Ph reductive cleavage of L(1) by lithium and s…

On the generation and degradation of emerged coral reef terrace sequences: First cosmogenic 36Cl analysis at Cape Laundi, Sumba Island (Indonesia)

2021

(IF 4.45: Q1); International audience; The emerged coral reef terrace sequence at Cape Laundi, on the north coast of Sumba Island (Indonesia), with at least 18 successive strandlines, remains poorly dated in spite of numerous previous data. The age discrepancies within these coral reef terraces (CRTs) were previously explained by their polycyclic nature, triggered by marine erosion and reoccupation of old coral colonies by new ones. This study aims at highlighting these processes, as well as the continental denudation that participates in the partial stripping of the thin superficial coral reef layer overlying the pre-existing surface, exhuming older coral colonies. For this purpose, we use…

2.14 Selected Diastereoselective Reactions: Enolate Alkylation

2012

This chapter discusses processes in which enolates are subjected to reaction with alkylating reagents. In all the processes examined here, at least one of the two reaction components is chiral and the reaction gives rise to one or more diastereomeric compounds. In most cases, the enolate is generated through deprotonation of the corresponding carbonyl precursor with a suitable base, but in several cases, the enolate is generated differently, for example, through Michael addition of a nucleophile to a conjugated carbonyl compound. The various factors that have been found to influence the stereochemical outcome of the alkylation reaction in a measurable way are also discussed. The material ha…

Enantiomeric separation of amphetamine and related compounds by liquid chromatography using precolumn derivatization witho-phthaldialdehyde

2002

The utility of the derivatization reagento-phthaldialdehyde (OPA) in combination with the chiral thiol N-acetyl-L-cysteine (NAC) for the enantioselective analysis of primary amphetamines and structurally related substances has been investigated. The diastereomers obtained have been chromatographed on an achiral, reversed phase C18 column (125 mm×4 mm i.d., 5 μm), and detected fluorimetrically. The influence of parameters affecting the chromatographic separation as well as the derivatization reaction has been optimized, using amphetamine, norephedrine, norepinephrine and 3,4-methylenedioxyamphetamine (MDA) as model compounds. On the basis of the results obtained, possible conditions for the …

Antibody-Capped Mesoporous Nanoscopic Materials: Design of a Probe for the Selective Chromo-Fluorogenic Detection of Finasteride

2012

[EN] The synthesis of capped mesoporous silica nanoparticles (MSN) conjugated with an antibody (AB) as a gatekeeper has been carried out in order to obtain a delivery system able to release an entrapped cargo (dye) in the presence of a target molecule (antigen) to which the conjugated antibody binds selectively. In particular, MSN loaded with rhodamine B and functionalized on the external surface with a suitable derivative of N-(t-butyl)- 3-oxo-(5a,17b)-4-aza-androst-1-ene-17-carboxamide (finasteride) have been prepared (S1). The addition of polyclonal antibodies against finasteride induced capping of the pores due to the interaction with the anchored hapten-like finasteride derivative to g…

Experimental Study on the Diet of Mosquitofish (Gambusia holbrooki) under Different Ecological Conditions in a Shallow Lake

2004

We studied the diet of the eastern mosquitofish Gambusia holbrooki with in situ experimental mesocosms located in a shallow lake. Different nutrient concentrations (phosphorus and nitrogen) and fish population densities were tested. Our results confirm that it is a planktivorous species, with also a great ingestion of algae and detritus. Nutrient fertilization caused almost no changes in this species feeding behavior, but larger mosquitofish stocks induced a shift to zooplanktivory and a decline in detritivory. When macrophytes were present, the predation effect focused on zooplankton and plant-associated animals, otherwise predation on bottom macroinvertebrates increased. Females preyed up…

Devocion à nuestra Señora de Suterraña de Nieva, que se venera en el Real Convento de Sto. Domingo de Nieva : es especial Abogada contra las tormenta…

Grav. xil. enmarcat de la Verge de la Soterraña La pàg. amb el grav. i el tít. orlada Text a dues col

Building materials and decay assessment of the Gerace Cathedral (Reggio Calabria, Southern Italy)

2023

A multi-analytical approach was employed for the first time to study the stone materials, wall paintings and related degradation forms in the Cathedral of Gerace (Reggio Calabria, southern Italy). With an area of around 1898 square meters, the Gerace Cathedral is the largest in Calabria: its construction dates back to the Norman era (between 1085 and 1120), and currently displays distinct features of Greek and Latin architectural orders. Despite having undergone numerous restorations, the church perfectly preserves its original buildings materials. Following an extensive site inspection campaign, supported by the experts dealing with building restoration, several areas were selected for ana…