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51.
Depending on the thermolytic conditions, dicobalthexacarbonyl-complexed enynes underwent cyclizations to provide different carbocyclic frameworks. Bicyclopentanones were formed from enyne-Co2(CO)6 complexes, or from enynes that were treated with Co2(CO)8, or more effectively, with Co4(CO)12 in an alcoholic solvent under a H2 or N2 atmosphere. This transformation proceeded via a sequential cyclocarbonylation and 1,4-reduction and is the first account using the cobalt carbonyl cluster. Under these conditions a cobalt hydride was presumably generated, which mediated reduction of the enone to the saturated ketone. In contrast, thermolysis of dicobalthexacarbonyl-complexed enynes under a hydrogen atmosphere in toluene resulted in their reductive cyclization to form monocyclic alkenes in moderate yields, in addition to the bicyclopentenone product. In some cases, addition of a hydrosilane to the reaction induced a complete suppression of the bicyclopentenone formation. While the former results demonstrate a reaction that occurs after the cycloaddition, the latter depicts another example of an interruption of the normal route in the Pauson-Khand reaction pathway. 相似文献
52.
Krafft ME Boñaga LV Felts AS Hirosawa C Kerrigan S 《The Journal of organic chemistry》2003,68(15):6039-6042
High levels of diastereoselection were achieved in the PKR of 1,6- and 1,7-cyclopropylidenynes bearing a bulky propargylic C(2)-symmetric acetal. 相似文献
53.
CpCo(CO)2-mediated cyclotrimerisation of bis-alkynes and cyanamides provides multisubstituted 2-aminopyridines, including macrocyclic products, such as 22 (50% yield). 相似文献
54.
C. Sola-Larrañaga 《Analytica chimica acta》2006,555(2):354-363
The concentrations of minerals (Na, K, P, Ca and Mg) and trace elements (Fe, Zn, Cu, Mn, Se, Al, Cd and Pb) in a total of 105 different infant formulae (starter, follow-up, premature, specialised and soya formulae) marketed in Spain were determined by atomic spectrometry (flame and electrothermal) and inductively coupled plasma emission spectroscopy after acid-microwave decomposition. On the basis of the elements distribution, a preliminary chemometric study with the use of pattern recognition methods was carried out. Hierarchical cluster analysis (HCA), principal component analysis (PCA), as unsupervised exploratory techniques, and linear discriminant analysis (LDA), were applied to characterise, classify and distinguish the different types of infant formulae. The HCA results showed that mineral and trace element content data support adequate information to obtain the infant formula differentiation. PCA permitted the reduction of 13 variables to four principal components accounting for 61.9% of the total variability. This four-factor model interprets reasonably well the correlations of these studied elements. The obtained element associations may be attributed to the composition of matrix ingredients, the contamination during elaboration, the additives and mineral supplements added and the present tendency of standardization in the manufacture of infant formulae. The application of LDA gave a 77.1% of infant formulae correctly assigned with three clearly differentiated and two overlapped groups. The use of discriminant functions, as a complementary tool, to distinguish the different types depending on protein matrix of infant formula, is also discussed. This survey shows that HCA, PCA and LDA techniques appear useful tools for the characterisation and classification of infant formulae using their elemental profile. 相似文献
55.
In this report we have shown that the commercially available Co(2)(CO)(8) and Co(4)(CO)(12), and enyne--Co(2)(CO)(6) complexes, are sufficiently effective in catalyzing the Pauson--Khand reaction under one atmosphere of CO pressure. It was further demonstrated that the efficiencies of these cyclization protocols could be enhanced by the presence of cyclohexylamine. These procedures have also rendered more practical and highly convenient alternatives for the catalytic Pauson--Khand reaction. Most importantly, we have dispelled the common belief that Co(4)(CO)(12) is inactive in the Pauson--Khand reaction under one atmosphere of carbon monoxide. Of mechanistic importance is that these studies have also shown that the probable formation of Co(4)(CO)(12) is not necessarily a dead end pathway in the Co(2)(CO)(8)-catalyzed Pauson--Khand reaction. It is also of interest that substoichiometric amounts of Co(2)(CO)(8), in DME and in the presence of cyclohexylamine, are sufficient for the cyclocarbonylation of enynes under a nitrogen atmosphere. Our findings have provided more practical protocols for the Pauson-Khand reaction using catalytic amounts of cobalt carbonyl complexes and a better understanding of the influence of Lewis bases on their efficiency. These reports on the activity of Co(4)(CO)(12) are anticipated to develop into a convenient and practical alternative for Co(2)(CO)(8) catalysis. 相似文献
56.
Huarte-Larrañaga F Aguilar A Lucas JM Albertí M 《The journal of physical chemistry. A》2007,111(33):8072-8079
The size-specific influence of the M+ alkali ion (M = Li, Na, K, Rb, and Cs) in the solvation process of the M+-benzene clusters by Ar atoms is investigated by means of molecular dynamic simulations. To fully understand the behavior observed in M+-bz-Ar(n) clusters, solvation is also studied in clusters containing either M+ or benzene only. The potential energy surfaces employed are based on a semiempirical bond-atom decomposition, which has been developed previously by some of the authors. The outcome of the dynamics is analyzed by employing radial distribution functions, studying the evolution of the distances between the Ar atoms and the alkali ion M+ or the benzene molecule for all M+-bz-Ar(n) clusters. For all members, in the M+-bz series, the benzene molecule (bz) is found to remain strongly bound to M+ even in the presence of solvent atoms. The radial distribution functions for the heavier clusters (K+-bz, Rb+-bz, and Cs+-bz), are found to be different than for the lighter (Na+-bz and Li+-bz) ones. 相似文献
57.
Larrañaga A Mesa JL Pizarro JL Lezama L Chapman JP Arriortua MI Rojo T 《Dalton transactions (Cambridge, England : 2003)》2005,(9):1727-1733
Two new manganese(II) selenite polymorphs with formula Mn(SeO3) have been synthesised using supercritical hydrothermal conditions. The crystal structure of both compounds (1) and (2) has been solved from single-crystal X-ray diffraction data. The structures consist of a three-dimensional framework formed by MnO6 octahedra and (SeO3)2- selenite anions with trigonal pyramidal geometry. Compound (1) shows chains of elongated, corner-sharing MnO6 octahedra. These chains are linked alternately by Mn2O10 dimers of edge-sharing octahedra. Conversely, compound (2) exhibits MnO6 octahedra sharing edges with three further octahedra, giving rise to a complex three-dimensional framework. The IR spectra show the characteristic bands of the selenite anion. Studies of luminescence and diffuse reflectance spectroscopy, performed at 6 K and at room temperature, respectively, have been carried out for both compounds. The Dq and Racah parameters are Dq= 830, B= 500 and C= 3790 cm(-1) for (1) and Dq= 795, B= 520 and C= 3785 cm(-1) for (2). The EPR spectra of both compounds are isotropic with a g-value of 1.99(1), which remains unchanged with variation in temperature. Magnetic measurements indicate the presence of antiferromagnetic couplings as the major interactions in both phases, but with compound (2) exhibiting at low temperature a canting of antiferromagnetically aligned spins. The estimated J-exchange parameters are J/k=-2.2 and -1.93 for (1) and (2), respectively, with J'= -0.87 and -0.55 K. 相似文献
58.
An approach for the calculation of initial-state-selected reaction probabilities utilizing a transition-state view and the multiconfigurational time-dependent Hartree approach is presented. Using flux correlation functions, wave packets located in the transition-state region are constructed and propagated into the asymptotic region to obtain initial-state-selected reaction probabilities. A complete set of reaction probabilities is obtained from a single set of thermal flux eigenstates. Concepts previously applied with success to the calculation of k(T) or N(E) are transferred to the calculation of state-selected probabilities. The benchmark H+H(2) (J=0) reaction on the LSTH potential-energy surface is used to test the reliability of this approach. 相似文献
59.
60.
M. Larrañaga M. D. Martin N. Gabilondo G. Kortaberria A. Eceiza C. C. Riccardi I. Mondragon 《Colloid and polymer science》2006,284(12):1403-1410
Nanostructuring of thermosetting systems using the concept of templating and taking advantage of the self-assembling capability of block copolymers is an exciting way for designing new materials for nanotechnological applications. In this first part of the work, reactive blends based on stoichiometric amounts of a diglycidylether of bisphenol-A epoxy resin and 4,4′-diaminodiphenylmethane cure agent modified with three poly(ethylene oxide)-co-poly(propylene oxide)-co-poly(ethylene oxide) block copolymers were studied. Cure advancement of these systems was analyzed by differential scanning calorimetry. The experimental results show a delay of cure rate, which increases as copolymer content and PEO molar ratio in the block copolymer rise. Infrared spectroscopy shows that PEO block is mainly responsible of physical interactions between the hydroxyl groups of growing epoxy thermoset and ether bonds of block copolymer. These interactions are mainly responsible for the delaying of cure kinetics. The molar ratio between blocks also has a critical influence on the delaying of the cure rate. A mechanistic approach of cure kinetics allows us to relate the delay of cure as a consequence of block copolymer adding to physical interactions between components. 相似文献