Metal complexes containing allenylidene and higher cumulenylidene ligands: a theoretical perspective

Transition metal complexes containing unsaturated carbenes have enjoyed a recent surge in research interest. In addition to showing potential as molecular wires and as components of opto-electronic materials, they provide multifaceted reactive sites for organic synthesis. In this Account, we describe results of recent theoretical studies that delineate the main features of electronic structure and bonding in allenylidenes and higher cumulenylidene complexes, [L(m)M]═C(═C)(n)═CR(1)R(2) (where L represents the ligand, M the metal, and n ≥ 1). Although free cumulenylidene ligands, :C(═C)(n)═CR(1)R(2), are extremely unstable and reactive species, they can be stabilized by coordination to a transition metal. The σ-donation of the electron lone pair on the terminal carbon atom to an empty metal d-orbital, together with the simultaneous π back-donation from filled metal d(π)-orbitals to empty cumulene π* system orbitals, leads to the formation of a strong M═C bond with multiple character. Density functional theory studies on the model systems [(CO)(5)Cr(═C)(n)CH(2)] and [trans-Cl(PH(3))(4)Ru(═C)(n)CH(2)](+) (where n = 1-9) have been useful in interpreting the structural and spectroscopic properties and the reactivity of this class of complexes. Geometry optimizations significantly contributed to the generalization of the sparse structural data available for allenylidene, butatrienylidene, and pentatetraenylidene complexes to higher cumulenylidene complexes (with up to eight carbon atoms in the chain), which show a clear structural trend. In particular, the geometries of all even-chain cumulenes are consistent with an almost purely cumulenic structure, whereas the geometries of odd-chain cumulenes present a significant polyyne-like carbon-carbon bond length alternation. The calculated bond dissociation energies (BDEs) of the cumulenylidene ligand remain almost constant on lengthening the cumulene chain. These BDEs indicate that there is no thermodynamic upper limit to the cumulene chain length and suggest that the synthetic difficulties in preparing higher cumulenylidenes are due to an increase in reactivity. The calculated charges on the carbon atoms show no significant polarization along the cumulene chain, indicating that charge distribution is not important in determining the regioselectivity of either electrophilic or nucleophilic attack, which is instead determined by frontier orbital factors. The breakdown of the contributions from the metal and the carbon atoms along the chain to the HOMO and LUMO shows that the HOMO has contributions mainly from the metal and the carbon atoms in even positions along the chain (C(2), C(4), C(6), and higher). In contrast, the LUMO has contributions mainly from the carbon atoms in odd positions along the chain (C(1), C(3), C(5), and higher), thus explaining the experimentally observed regioselectivity of electrophilic and nucleophilic attacks, which are directed, respectively, to even and odd positions of the cumulenylidene chain. The study of the electronic structure of cumulenylidenes has allowed us not only to give a consistent rationale for the main structural and spectroscopic properties and for the reactivity of this emerging class of compounds but also to predict the effect of ancillary ligands on the metal center or substituents on the carbon end. The result is a useful guide to new developments in the still-underexplored fields of this fascinating class of compounds.     

Granular self-organisation and reactivity—adsorbates and agglomerates particle size influence

The aim of this work is to study the organisation of the distributed system and the influence of adsorption and agglomeration phenomena in a dry bi-phase mixture. The studied system is a mixture of silica and carbonate. The parameter of interest is particle size. With the crossover of different fractions of silica and carbonate, it is possible to build a dimensional chessboard and then study the role of dimension in the organisation of distributed system. In these mixtures, several combinations are possible following the particle size. These combinations result from agglomeration and adsorption mechanisms. It is necessary to distinguish self-attractive phenomena (self-agglomeration and self-adsorption) that concern particles of same chemical composition, and inter-attractive phenomena (inter-agglomeration and inter-adsorption) that concern particles of different chemical compositions. The reactivity of the different mixtures treated thermally at 850 °C is measured by X-ray diffraction (DRX). It is estimated by the quantity of produced phases. Then this reactivity is explained by the different attractive phenomena studied.     

Sol–Gel Synthesis of λ–Na2O·xAl2O3 Films

Na₂O· x Al₂O₃ ( x = 9, 11)films have been obtained by sol–gel method. Crystallization processes during heat treatments have been investigated by X–ray diffraction analysis. A metastable phase with the mullite structure, λ–Na₂O· x Al₂O₃, has been observed starting from 800°C. Films remained stable after a heat treatment at 1000°C for 250 h. Impedance spectroscopy measurements showed that the films of λ-Na₂O· x Al₂O₃ possess a large three–dimensional ionic conductivity at 400°C.     

Recycled poly(ethylene terephthalate) and its short glass fibres composites: effects of hygrothermal aging on the thermo-mechanical behaviour

This paper reports on the effects of hygrothermal aging at 70 °C in water and at 80% relative humidity, on the thermo-mechanical properties, molar mass and microstructure of recycled poly(ethylene terephthalate) (rPET) and its short glass fibres composites.For all the investigated materials, the elastic mechanical properties (tensile and storage moduli) determined at low strain levels resulted practically unaffected by hygrothermal aging under the selected conditions. On the other hand, a marked reduction of the tensile strength and apparent fracture toughness has been observed for rPET matrix and its composites during hygrothermal aging, more markedly for materials immersed in water than for those aged at 80% RH. Both properties resulted to be related on the molar mass of the rPET matrix, that decreased during hygrothermal aging as a consequence of the hydrolysis process.The materials glass transition, evaluated as the temperature of the loss factor peak, increased during hygrothermal aging due to the progressively restricted mobility of the amorphous phase caused by a concurrent crystallinity increase. This crystallization process (chemicrystallization) is favoured by temperature, by the plasticizing effect of water and by the reduction of molar mass.Consistently with the mechanical measurements, the morphology of fracture surfaces exposed to hygrothermal aging in water revealed a reduction of plastic deformation of the rPET matrix and a weakening of the fibre-matrix interface for rPET composites.     

Oxygen Storage Behavior of Ceria–Zirconia-Based Catalysts in the Presence of SO2

This paper investigates the effect of the presence of SO₂ in the dynamics of oxygen storage on ceria and ceria–zirconia. The introduction of SO₂ under reaction conditions at T<873 K negatively affects CO conversion under oscillating conditions on all the supports studied, owing to the formation of sulfate species. Deactivation is observed on all supports and activity is recovered only after desorption of SO₂, which occurs at 950<T<1000 K, depending on catalyst composition (Ce/Zr ratio) and treatment atmosphere. The amount of sulfur adsorbed is higher over solid solutions, reaching a maximum with Ce _x Zr_1–x O₂ (0.5<x<0.68). However this does not adversely affect activity compared to ceria. In the presence of Rh and Pd, reactivation is favored under reaction conditions. More generally, it appears that the removal of sulfates is facilitated in reductive atmospheres (both hydrogen and CO) over mixed oxides. No differences are observed following regeneration under oxidizing conditions.     

On the possibility of rhenium clustering in nickel-based superalloys

In order to elucidate the role of this element in superalloy metallurgy, the binding energy of Re–Re pairs and the stability of small Re clusters in the nickel face-centred cubic (fcc) lattice is investigated using ab initio density functional theory. It is shown that the formation of Re–Re nearest neighbour pairs is energetically unfavourable, and that this repulsive energy is dramatically reduced as soon as the solute atoms move further apart from one another. Furthermore, small nearest neighbour and second neighbour Re clusters are found to be unstable. The calculations are repeated for W and Ta, which lie beside Re in the periodic table; the results are essentially the same, except that some Ta–Ta higher order pairs have a positive binding energy, consistent with the Ni–Ta binary phase diagram exhibiting several ordered intermetallics. The predictions show that Re clusters are unstable in fcc Ni and it is unlikely that clustering has a role in improving creep and fatigue properties (the rhenium-effect) in Ni-based superalloys.     

ZSM-5 zeolite films on Si substrates grown by in situ seeding and secondary crystal growth and application in an electrochemical hydrocarbon gas sensor

ZSM-5 zeolite films were grown on Si substrates by a two-step hydrothermal synthesis consisting of in situ seeding and secondary crystal growth. The films were 8–13 μm thick and partly oriented with the c-axis perpendicular to the substrate surface. After ion exchange with sodium ions, one film was applied as solid electrolyte in a potentiometric hydrocarbon gas sensor. A fast and reversible voltage response of the sensor to varying propane concentrations (100 ppm – 10%) was observed in O₂/CO₂/N₂ gas mixtures at 723 K.     

High and low surface area NiO–MgO and CoO–MgO solid solutions: a study of XPS surface composition and CO oxidation activity

Oxide solid solutions NiO–MgO of high surface area were studied by XPS. The surface Ni²⁺ concentration was found to be equal, within experimental errors, to the bulk concentration. The result is analogous to that found previously for the low surface area NiO–MgO system and for both the high and low surface area systems of CoO–MgO. The catalytic oxidation of CO by O₂, on high and low surface area NiO–MgO and CoO–MgO materials, was investigated with the aim of relating the catalytic activity with transition metal ion nature and concentration. Turnover frequency data (CO₂ molecules produced per second per surface atom) show that the activity is due primarily to the transition metal ions and is not subject to the ions being in special configurations (dimers or trimers) or in special positions (edges, corners). The activity of CoO–MgO is higher than that of NiO–MgO solid solution. This revised version was published online in June 2006 with corrections to the Cover Date.     

Development of a hydraulic control mechanism for cyclic pitch marine current turbines

Tidal power generation by means of marine current farms is potentially a large renewable energy resource which could be harnessed in many coastal waters. Its availability is highly predictable in time, and the technology promises high energy conversion efficiency along with a relatively low impact on sea life due to its relatively small disturbance of natural tidal flows.A series of devices have so far been proposed and developed for the extraction and conversion of kinetic energy present in tidal flows into useful electrical power [1]. Designs include horizontal axis turbines, vertical axis turbines, and devices with oscillating lift surfaces. Up to date no technology has firmly established itself.This paper describes a novel hydraulic control mechanism designed for vertical-axis marine current turbines of the straight-bladed Darrieus type. It has been found to significantly improve turbine efficiency over conventional Darrieus turbines when operated at low blade tip-speed to tidal-flow-velocity ratios (TSR) and to give the turbine the ability to self-start reliably. The control mechanism enforces a cyclic pivoting motion on the turbine blades as they move around their circular flight-path. The movement of the pitch control is of sinusoidal shape and is continuously variable in amplitude. The blade actuation is powered by the turbine's own rotation and is implemented using a swash-plate mechanism in conjunction with a hydraulic circuit for every blade. For surface piercing turbines, this control mechanism may be remotely positioned in a dry nacelle above sea level. If the appropriate design is applied, this can offer access to the cyclic pitch control mechanism, gearbox and generator, even when the turbine is operational, promising lower maintenance and operating costs compared with submerged systems.     

Integrated Approach for Supporting Sustainable Water Resources Management of Irrigation Based on the WEFN Framework

Irrigated agriculture plays a vital role for the socio-economic development of the Mediterranean area, although it has significant impacts on both water and energy resources. Therefore, in a context in which water resources are also experiencing increasing pressures, there is an urgent need for supporting their sustainable management. This may be an extremely challenging task, especially at the local scale, due to the several interconnected dynamics affecting the state of a complex irrigation system. In fact, multiple actors are involved in decision-making processes, and the use of natural resources (and their mutual interactions) strongly depends on their behaviors, which affect the system as a whole. In this context, the present study proposes an integrated methodology, based on the Water Energy Food Nexus (WEFN), specifically focused on the sustainable management of water resources for irrigation. Firstly, a model based on Causal Loop Diagrams (CLD) is developed in order to get a deep insight into the key dynamics behind a complex irrigation system. Secondly, three indices based on the “footprint” concept are identified, in order to synthesize such dynamics. The integration of these two approaches support investigating the whole system and, particularly, understanding the influence of multiple decisional actors on it, as well as the role of a set of key drivers and constraints. This might also allow drawing some relevant conclusions, useful for supporting effective decisions oriented to a sustainable water resources management. Specific reference is made to a case study, the Capitanata irrigation system, located in the Southern Italy.