Investigations on the coupling of ethylene and alkynes in [IrTp Me2] compounds: water as an effective trapping agent

The reaction of the bis(ethylene) complex [Tp(Me(2) )Ir(C(2)H(4))(2)] (1) (Tp(Me(2) ): hydrotris(3,5-dimethylpyrazolyl)borate) with two equivalents of dimethyl acetylenedicarboxylate (DMAD) in CH(2)Cl(2) at 25 degrees C gives the hydride-alkenyl species [Tp(Me(2) )IrH{C(R)=C(R)C(R)=C(R)CH=CH(2)}] (2, R: CO(2)Me) in high yield. A careful study of this system has established the active role of a number of intermediates en route to producing 2. The first of these is the iridium(I) complex [Tp(Me(2) )Ir(C(2)H(4))(DMAD)] (4) formed by substitution of one of the ethylene ligands in 1 by a molecule of DMAD. Complex 4 reacts further with another equivalent of the alkyne to give the unsaturated metallacyclopentadiene [Tp(Me(2) )Ir{C(R)=C(R)C(R)=C(R)}], which can be trapped by added water to give adduct 7, or can react with the C(2)H(4) present in solution generating complex 2. This last step has been shown to proceed by insertion of ethylene into one of the Ir--C bonds of the metallacyclopentadiene and subsequent beta-H elimination. Complex 1 reacts sequentially with one equivalent of DMAD and one equivalent of methyl propiolate (MP) in the presence of water, with regioselective formation of the nonsymmetric iridacyclopentadiene [Tp(Me(2) )Ir{C(R)=C(R)C(H)=C(R)}(H(2)O)] (9). Complex 9 reacts with ethylene giving a hydride-alkenyl complex 10, related to 2, in which the C(2)H(4) has inserted regiospecifically into the Ir--C(R) bond that bears the CH functionality. Heating solutions of either 2 or 10 in CH(2)Cl(2) allows the formation of the allyl species 3 or 11, respectively, by simple stereoselective migration of the hydride ligand to the Calpha alkenyl carbon atom and concomitant bond reorganization of the resulting organic chain. All the compounds described herein have been characterized by microanalysis, IR and NMR spectroscopy, and for the case of 3, 7, 7CO, 8NCMe, 9, 9NCMe, and 10, also by single-crystal X-ray diffraction studies.     

Diastereoselective synthesis of 2-aryl-3-vinyl-2,3-dihydrobenzo[b]furans through a Sakurai reaction: a mechanistic proposal

The condensation of 2,3-dihydrobenzoxasilepins with aromatic aldehydes in the presence of boron trifluoride to form 2,3-dihydrobenzofurans shows a level of diastereoselection which is a function of the electronic nature of the aldehyde and the polarity of the solvent. The study of the mechanism of the reaction demonstrated that it proceeds through a ring-opened allylfluorosilane, which is stable enough to be isolated and characterized.     

Transition metal bisdithiolene complexes based on extended ligands with fused tetrathiafulvalene and thiophene moieties: new single-component molecular metals

The gold and nickel bisdithiolene complexes based on new highly extended ligands incorporating fused tetrathiafulvalene and thiophene moieties (alpha-tdt=thiophenetetrathiafulvalenedithiolate and dtdt=dihydro- thiophenetetrathiafulvalenedithiolate), were prepared and characterised by using cyclic voltammetry, single crystal X-ray diffraction, EPR, magnetic susceptibility and electrical transport measurements. These complexes, initially obtained under anaerobic conditions as diamagnetic gold monoanic [nBu(4)N][Au(alpha-tdt)(2)] (4), [nBu(4)N][Au(dtdt)(2)] (3) and nickel dianionic species [(nBu(4)N)(2)][Ni(alpha-tdt)(2)] (8), [(nBu(4)N)(2)][Ni(dtdt)(2)] (7), can be easily oxidised to the stable neutral state just by air or iodine exposure. The monoanionic complexes crystallise in at least two polymorphs, all of which have good cation and anion segregation in alternated layers, the anion layers making a dense 2D network of short SS contacts. All of the neutral complexes, obtained as microcrystalline or quasi amorphous fine powder, present relatively large magnetic susceptibilities that correspond to effective magnetic moments in the range 1-3 mu(B) indicative of high spin states and very high electrical conductivity that in case of the Ni compound can reach sigma(RT) approximately 250 S cm(-1) with a clear metallic behaviour. These compounds are new examples of the still rare single-component molecular metals.     

Cyclic tetranuclear and hexanuclear palladium(II) complexes and their host-guest chemistry

Cyclic tetrameric complexes have been prepared by the reaction of Pd(en)Cl2 or Pd(dapol)Cl2, or their nitrato analogues, with Na2(5'GMP) in aqueous solution, where en=1,2-diaminoethane, dapol=1,3-diamino-2-propanol, and 5'GMP=guanosine 5'-monophosphate. Addition of certain small molecules containing hydrophobic groups resulted in the expansion of the tetramer to a cyclic hexamer with strong bonding of one guest per hexameric host. At pH 5-6, the guest molecule can be a cation, anion, or neutral, and those species containing trimetylsilyl and t-butyl groups bonded the most strongly. The size of the central cavity of the [Pd(en)(5'GMP)]6 host has been estimated to be 5.2 A. Formation of the host-guest complex caused a large upfield shift (Deltadelta) of 2.5-2.9 ppm in the 1H NMR spectrum of the most highly affected guest protons, which were those in closest proximity to the guanine nucleobases. NOESY spectra were used to determine the interaction sites between the host and the guest. Apparent association constants determined at 26 degrees C and pD 5.4 for the [Pd(en)(5'GMP)]6-DSS and [Pd(en)(5'GMP)]6-t-butanol systems, where DSS is 3-(trimethylsilyl)-1-propanesulfonate anion, were 1.36+/-0.11x10(4) and 2.74+/-0.95x10(4) M(-3/2), respectively. The Pd(dapol)-5'GMP system forms hexameric host-guest complexes, similar in nature to those of the Pd(en)-5'GMP system. The molecular and crystal structures of Pd(dapol)Cl2 are also reported.     

Determination of azoxystrobin residues in grapes, musts and wines with a multicommuted flow-through optosensor implemented with photochemically induced fluorescence

In this paper, the conversion of azoxystrobin in a strongly fluorescent degradation product by UV irradiation with quantitative purposes and its fluorimetric determination are reported for the first time. A multicommuted flow injection-solid phase spectroscopy (FI-SPS) system combined with photochemically-induced fluorescence (PIF) is developed for the determination of azoxystrobin in grapes, must and wine. Grape samples were homogenized and extracted with methanol and further cleaned-up by solid-phase extraction on C₁₈ silica gel. Wine samples were solid-phase extracted on C₁₈ sorbent using dichloromethane as eluent. Recoveries of azoxystrobin from spiked grapes (0.5-2.0 mg Kg⁻¹), must (0.5-2.0 μg mL⁻¹) and wine (0.5-2.0 μg mL⁻¹) were 84.0-87.6%, 95.5-105.9% and 88.5-111.2%, respectively. The quantification limit for grapes was 0.021 mg Kg⁻¹, being within European Union regulations, and 18 μg L⁻¹ and 8 μg L⁻¹ for must and wine, respectively.     

Synthesis, crystal-structure determination and magnetic properties of two new transition-metal carbodiimides: CoNCN and NiNCN

Synthesis, structure determination, and magnetic properties are reported for the metastable and crystal-chemically isotypic phases cobalt carbodiimide, CoNCN, and nickel carbodiimide, NiNCN, adopting the hexagonal system and space group P63/mmc (NiAs type) with interatomic distances of Co-N = 2.17 Angstrom and Ni-N = 2.12 Angstrom and an octahedral coordination of the transition-metal ions; the NCN(2-) units reveal the carbodiimide shape with two C=N double bonds. The low-susceptibility data go back to strong antiferromagnetic spin-spin coupling, similar to the behavior of the electronically related oxides CoO and NiO.     

A Bayesian approach to assess data from radionuclide activity analyses in environmental samples

A Bayesian statistical approach is introduced to assess experimental data from the analyses of radionuclide activity concentration in environmental samples (low activities). A theoretical model has been developed that allows the use of known prior information about the value of the measurand (activity), together with the experimental value determined through the measurement. The model has been applied to data of the Inter-laboratory Proficiency Test organised periodically among Spanish environmental radioactivity laboratories that are producing the radiochemical results for the Spanish radioactive monitoring network. A global improvement of laboratories performance is produced when this prior information is taken into account. The prior information used in this methodology is an interval within which the activity is known to be contained, but it could be extended to any other experimental quantity with a different type of prior information available.     

Synthesis and acid digestion of biomorphic ceramics: determination of alkaline and alkaline earth ions

Ceramic and glass are some of the more recent engineering materials and those that are most resistant to environmental conditions. They belong to advanced materials in that they are being developed for the aerospace and electronics industries. In the last decade, a new class of ceramic materials has been the focus of particular attention. The materials were produced with natural, renewable resources (wood or wood-based products). In this work, we have synthesised a new biomorphic ceramic material from oak wood and Si infiltration. After the material characterization, we have optimized the dissolution of the sample by acid attack in an oven under microwave irradiation. Experimental designs were used as a multivariate strategy for the evaluation of the effects of varying several variables at the same time. The optimization was performed in two steps using factorial design for preliminary evaluation and a Draper-Lin design for determination of the critical experimental conditions. Five variables (time, power, volume of HNO3, volume H2SO4 and volume of HF) were considered as factors and as a response the concentration of different metal ions in the optimization process. Interactions between analytical factors and their optimal levels were investigated using a Draper-Lin design.     

Synthesis, crystal structure, aqueous speciation, and kinetics of substitution reactions in a water-soluble Mo3S4 cluster bearing hydroxymethyl diphosphine ligands

The [Mo3S4Cl3(dhmpe)3]Cl ([1]Cl) cluster has been prepared from [Mo3S7Cl6]2- and the water-soluble 1,2-bis(bis(hydroxymethyl)-phosphino)ethane (dhmpe, L) ligand. The crystal structure has been determined by X-ray diffraction methods and shows the incomplete cuboidal structure typical of the M3Q4 clusters (M=Mo, W; Q=S, Se), with a capping sulfide ligand to the three metal centers and the other three sulfides acting as bridges between two Mo atoms. The octahedral coordination around each metal center is completed with a chlorine and two phosphorus atoms of one L ligand. The chemistry of aqueous solutions of [1]Cl is dominated by the formation of the [Mo3S4L(L-H)2(H2O)]2+ complex ([2]2+), where the three chlorides have been replaced by one water molecule and two alkoxo groups of two different dhmpe ligands, thus leading to a solution structure where the three metal centers are not equivalent. A detailed study based on stopped-flow, 31P{1H} NMR, and electrospray ionization mass spectrometry techniques has been carried out to understand the behavior of [2]2+ in aqueous solution. In this way, it has been established that the addition of an excess of X- (Cl-, SCN-) leads to [Mo3S4X3(dhmpe)3]+ complexes in three resolved kinetic steps that correspond to the sequential coordination of X- at the three metal centers. However, whereas the first two steps involve the opening of the chelate rings formed with the alkoxo groups of the dhmpe ligands, the third one corresponds to the substitution of the coordinated water molecule. These results demonstrate that the asymmetry introduced by the closure of chelate rings at only two of the three Mo centers makes the kinetics of the reaction deviate significantly from the statistical behavior typically associated with M3Q4 clusters. The results obtained for the reaction of [2]2+ with acid and base are also described, and they complete the picture of the aqueous speciation of this cluster.     

Defects in divided zinc-copper aluminate spinels: structural features and optical absorption properties

Zn1-xCuxAl2O4 (0 < or = x < 0.30) compounds have been synthesized by polyesterification using metallic salts and annealing at low temperatures as well as by conventional solid state. XRD-powder data refinements (Rietveld method) have demonstrated that both compound series crystallize in the spinel structure (Fd3m) and exhibit similar inversion rates. This low-temperature route lead to metastable phases with crystallite sizes around 40 nm whereas particle sizes are larger than 1 moicrom in the case of solid-state route. This preparative method largely described in the literature allows stabilizing reduced copper states thanks to the presence of reductive organic species, which are decomposed below T = 700 degrees C. The absorption spectra of the x = 0.15 composition exhibit strong differences depending on the synthesis route. These differences can be explained by the occurrence of Cu2+/Cu+ mixed valencies in compounds prepared by the low-temperature route; 33% of monovalent copper has been identified in the x = 0.15 composition prepared by low-temperature process, whereas the solid-state compound contains only divalent copper. Reductive properties of polyesterification reaction implying citric acid and low annealing temperature (T = 700 degrees C) are mainly responsible of the occurrence of the Cu2+/Cu+ mixed valencies. Actually, the annealing under air at T = 1000 degrees C of divided zinc-copper aluminates prepared at low temperatures (T = 700 degrees C) leads to the oxidation reaction Cu+ --> Cu2+ + e- confirmed by the evolution of magnetic measurements, ESR spectra, and optical absorption properties. Defects such as oxygen vacancies in the anionic network leading to reduction in the cations coordination number could also explain the strong evolution of optical absorption spectra especially around lambda = 700 nm where intervalencies transfer (Cu+/Cu2+) as well as intra-atomic d-d transitions (Cu2+ in a 5-fold coordination) can occur. Finally the occurrence of monovalent and divalent copper at the surface of such divided oxides, probably in tetrahedral sites, has been demonstrated by FTIR spectroscopy using the co-adsorption of CO and NO as probe molecules.