Unravelling the reaction path of rhodium-MonoPhos-catalysed olefin hydrogenation

The mechanism of the asymmetric hydrogenation of methyl (Z)-2-acetamidocinnamate (mac) catalysed by [Rh(MonoPhos)(2)(nbd)]SbF(6) (MonoPhos: 3,5-dioxa-4-phosphacyclohepta[2,1-a:3,4-a']dinaphthalen-4-yl)dimethylamine) was elucidated by using (1)H, (31)P and (103)Rh NMR spectroscopy and ESI-MS. The use of nbd allows one to obtain in pure form the rhodium complex that contains two units of the ligand. In contrast to the analogous complexes that contain cis,cis-1,5-cyclooctadiene (cod), this complex shows well-resolved NMR spectroscopic signals. Hydrogenation of these catalyst precursors at 1 bar total pressure gave rise to the formation of a bimetallic complex of general formula [Rh(MonoPhos)(2)](2)(SbF(6))(2); no solvate complexes were detected. In the dimeric complex both rhodium atoms are ligated to two MonoPhos ligands but, in addition, each rhodium atom also binds to one of the binaphthyl rings of a ligand that is bound to the other rhodium metal. Upon addition of mac, a mixture of diastereomeric complexes [Rh(MonoPhos)(2)(mac)]SbF(6) is formed in which the substrate is bound in a chelate fashion to the metal. Upon hydrogenation, these adducts are converted into a new complex [Rh(MonoPhos)(2){mac(H)(2)}]SbF(6) in which the methyl phenylalaninate mac(H)(2) is bound through its aromatic ring to rhodium. Addition of mac to this complex leads to displacement of the product by the substrate. No hydride intermediates could be detected and no evidence was found for the involvement at any stage of the process of complexes with only one coordinated MonoPhos. The collected data suggest that the asymmetric hydrogenation follows a Halpern-like mechanism in which the less abundant substrate-catalyst adduct is preferentially hydrogenated to phenylalanine methyl ester.     

Hybrid organo-inorganic clay with nonionic interlayers. mid- and near-IR spectroscopic studies

The intercalation of organic polymers molecules (i.e., PEGs and BRIJ) into a standard Ca-montmorillonite has been studied by XRD, TG, and IR spectroscopy. The polymer intercalation is confirmed by the increasing of the d(001) in XRD spectra as well as by the complex multisteps thermal decomposition behavior of the organo-clay materials. Mid-IR and diffuse reflectance near-IR spectra of the intercalated materials show the polymer diagnostic bands (CH stretching and deformation mode), shifted or changed in shape by the interaction with the clay matrix. Both PEG 1500 and PEG 4000 based materials are likely intercalated in an extended configuration, similar to the amorphous polymer form. BRIJ intercalated polymer spectra suggest the disordered conformation of the alkilic chain in a prevailing "gauche", poorly packed, conformation. Host montmorillonite IR bands, mainly OH and water stretching and deformation fundamentals, combination, and overtone bands, are reduced in intensity by polymer intercalation, pointing out an interaction, likely through H-bonding and/or a possible substitution of cations hydration water molecules.     

Failure of n‐uniqueness: a family of examples

In this paper, the connections between model theory and the theory of infinite permutation groups (see 11 ) are used to study the n‐existence and the n‐uniqueness for n‐amalgamation problems of stable theories. We show that, for any n ? 2, there exists a stable theory having (k + 1)‐existence and k‐uniqueness, for every k ? n, but has neither (n + 2)‐existence nor (n + 1)‐uniqueness. In particular, this generalizes the example, for n = 2, due to Hrushovski given in 3 . © 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim     

Performance evaluation of shared and separate inverted files

In this paper, two different structures for inverted files are analyzed and compared, when the relational join operation is taken into account. The structures are called shared and separate inverted files. The results are given of some experiments which show that the shared inverted organization is always advantageous when the inverted files are not sorted and is almost always advantageous when the files are sorted.     

The role of Mg complexes in the degradation of InGaN-based LEDs

The electrical and optical properties of commercial blue InGaN-based LEDs after room temperature aging tests at DC-forward currents from 50 to 100 mA are studied by Current–Voltage, Capacitance–Voltage, Electroluminescence and Cathodoluminescence techniques. An increase of the reverse and low-bias forward currents, of the parasitic series resistance and a substantial optical intensity reduction are observed in all the devices investigated with or without heat sink. In addition, only in devices aged at 100 mA without heat sink, the onset of a broad optical band peaked at about 3.1 eV and an apparent doping decrease of about four times, as obtained by Capacitance–Voltage measurements, are found. Temperature-dependent luminescence analyses show the quenching of the 3.1 eV band above 200 K, suggesting its donor–acceptor-pair nature. The band onset is interpreted as a result of the Mg dopant instability in the p-type layers, correlated to the device self-heating inducing junction temperature above 300 C. The band is attributed to Mg-related metastable complexes, such as Mg–H₂, acting as shallow acceptors. Due to their unstable nature, the behaviour of the 3.1 eV emission is studied under controlled electron-beam irradiation in the SEM. Its time evolution during 60 min of irradiation reveals an almost complete quenching in the Cathodoluminescence spectra, which is attributed to the dissociation of the Mg–H₂ complexes.     

Copper(II) complexes of diamino-diamido-type ligands as chiral eluents in the enantiomeric separation of D,L-dansylamino acids by reversed-phase high-performance liquid chromatography

For purpose of studying the mechanism of chiral recognition in high-performance liquid chromatography (HPLC) (reversed phase), a model system is proposed, i.e., copper(II) complexes of diamino-diamido-type ligands containing L-amino acids (AA-NN-n) which added to the eluent are able to perform the enantiomeric resolution of dansylamino acids on C8 and C18 columns. Being potentially tetradentate, this system should be more liable to give an apical or outer-sphere interaction with the enantiomer rather than a simultaneous dechelation of two binding sites, as in the classical ligand-exchange mechanism. This model allows the variation of several parameters, such as the structural and electronic features of the initial complexes, their relative stabilities and lipophilicities and their correlation with enantioselectivity in HPLC.     

Oxalate films and red stains on Carrara marble

The analytical studies carried out during two different diagnostic surveys, respectively in 1983 and 2003, offered the opportunity to control decay phenomena development on stones facing Certosa of Pavia (Italy). Calcium oxalate films and red stains, present on Carrara marble surface, have been particularly focused; these are the only decay phenomena which apparently have remained unchanged during a period of twenty years. More sensitive and in-depth analytical studies (FTIR equipped with diamond cell, GC-MS, SEM-EDS and optical microscopy) achieved a better knowledge about their composition. Results allowed a critical evaluation of the role of oxalate films on the external marble surface and to suggest new hypotheses about the formation of red stains.