Ferrocene-Based Pyridylphosphine Ligands – Coordination Chemistry of Group 10, 11 and 12 Metals

English: The present thesis describes the synthesis of 1,1’-ferrocendiyl-based pyridylphosphine ligands, the exploration of their fundamental coordination chemistry and preliminary experiments with selected complexes aimed at potential applications. One main aspect is the synthesis of the bidentate ferrocene-based pyridylphosphine ligands 1-(Pyrid-2-yl)-1’-diphenylphosphinoferrocene, 1-(Pyrid-3-yl)-1’-diphenylphosphinoferrocene and 1-[(Pyrid-2-yl)methyl]-1’-diphenylphosphinoferrocene. A specific feature of these ligands is the ball-bearing like flexibility of the ferrocenebased backbone. An additional flexibility element is the rotation around the C–C single bonds. Consequently, the donor atoms can realise a wide range of positions with respect to each other and are therefore able to adapt to the coordination requirements of different metal centres. The flexibility of the ligand also plays a role in another key aspect of this work, which concerns the coordination mode, i. e. bridging vs. chelating. In addition to the flexibility, also the position of the donor atoms to each other is important. This is largely affected by the position of the pyridyl nitrogen (pyrid-2-yl vs. pyrid-3-yl) and the methylen group in 1-[(Pyrid-2-yl)methyl]-1’-diphenylphosphinoferrocene. Another interesting point is the combination of a soft phosphorus donor atom with a harder nitrogen donor atom, according to the HSAB principle. This combination generates a unique binding profile, since the pi-acceptor character of the P site is able to stabilise a metal centre in a low oxidation state, while the nitrogen sigma-donor ability can make the metal more susceptible to oxidative addition reactions. A P,N-donor combination can afford hemilabile binding profiles, which would be ideal for catalysis. Beyond 1,2-substituted ferrocene derivatives, which are quite successful in catalytic applications, 1,1’-derivatives are rather underrepresented. While a low-yield synthetic pathway to 1-(Pyrid-2-yl)-1’-diphenylphosphinoferrocene was already described in the literature [I. R. Butler, Organometallics 1992, 11, 74.], it was possible to find a new, improved and simplified synthetic pathway. Both other ligands were unknown prior to this work. Satisfactory results in the synthesis of 1-(Pyrid-3-yl)-1’-diphenylphosphinoferrocene could be achieved by working in analogy to the new synthetic procedure for 1-(Pyrid-2-yl)-1’-diphenylphosphinoferrocene. The synthesis of 1-[(Pyrid-2-yl)methyl]-1’-diphenylphosphinoferrocene has been handled by the group of Prof. Petr Stepnicka from Charles University, Prague, Czech Republic. The synthesis of tridentate ligands with an analogous heterodentate arrangement, was investigated briefly as a sideline of this study. The major part of this thesis deals with the fundamental coordination chemistry towards transition metals of the groups 10, 11 and 12. Due to the well-established catalytic properties of analogous palladium complexes, the coordination chemistry towards palladium (group 10) is of particular interest. The metals zinc and cadmium (group 12) are also of substantial importance because they are redox-inert in their divalent state. This is relevant in view of electrochemical investigations concerning the utilisation of the ligands as molecular redox sensors. Also mercury and the monovalent metals silver and gold (group 11) are included because of their rich coordination chemistry. It is essential to answer questions concerning aspects of the ligands’ coordination mode bearing in mind the HSAB principle.

Many-body theory of laser-induced ultrafast demagnetization and angular momentum transfer in ferromagnetic transition metals

An electronic theory is developed, which describes the ultrafast demagnetization in itinerant ferromagnets following the absorption of a femtosecond laser pulse. The present work intends to elucidate the microscopic physics of this ultrafast phenomenon by identifying its fundamental mechanisms. In particular, it aims to reveal the nature of the involved spin excitations and angular-momentum transfer between spin and lattice, which are still subjects of intensive debate. In the first preliminary part of the thesis the initial stage of the laser-induced demagnetization process is considered. In this stage the electronic system is highly excited by spin-conserving elementary excitations involved in the laser-pulse absorption, while the spin or magnon degrees of freedom remain very weakly excited. The role of electron-hole excitations on the stability of the magnetic order of one- and two-dimensional 3d transition metals (TMs) is investigated by using ab initio density-functional theory. The results show that the local magnetic moments are remarkably stable even at very high levels of local energy density and, therefore, indicate that these moments preserve their identity throughout the entire demagnetization process. In the second main part of the thesis a many-body theory is proposed, which takes into account these local magnetic moments and the local character of the involved spin excitations such as spin fluctuations from the very beginning. In this approach the relevant valence 3d and 4p electrons are described in terms of a multiband model Hamiltonian which includes Coulomb interactions, interatomic hybridizations, spin-orbit interactions, as well as the coupling to the time-dependent laser field on the same footing. An exact numerical time evolution is performed for small ferromagnetic TM clusters. The dynamical simulations show that after ultra-short laser pulse absorption the magnetization of these clusters decreases on a time scale of hundred femtoseconds. In particular, the results reproduce the experimentally observed laser-induced demagnetization in ferromagnets and demonstrate that this effect can be explained in terms of the following purely electronic non-adiabatic mechanism: First, on a time scale of 10–100 fs after laser excitation the spin-orbit coupling yields local angular-momentum transfer between the spins and the electron orbits, while subsequently the orbital angular momentum is very rapidly quenched in the lattice on the time scale of one femtosecond due to interatomic electron hoppings. In combination, these two processes result in a demagnetization within hundred or a few hundred femtoseconds after laser-pulse absorption.

Metals.

El estudio de los metales y las reacciones entre ellos forma parte de la química. Este texto nos permite conocer cómo ésta se desarrolla no sólo en los laboratorios y entre científicos, sino también en fábricas y plantas químicas, y con múltiples aplicaciones: en la fabricación de fibras sintéticas para los tejidos, de explosivos para los fuegos artificiales, de disolventes para las pinturas, de fertilizantes para los cultivos y de medicamentos para tratar enfermedades.

The reactions of metals.

Explica que son los metales, sus propiedades, las aleaciones, y las reacciones que se producen con otros materiales, lo que los científicos llaman reactividad. Está adaptado a alumnos de once a catorce años, que cursan la etapa 3 (Key Stage 3)del curriculo nacional inglés.

Valorisation of industrial wastes for the removal of metals and arsenic from aqueous effluents

En la presente tesis se han realizado estudios de eliminación de metales pesados y arsénico de aguas contaminadas mediante procesos de adsorción sobre materiales de bajo coste. Dichos materiales son, en todos los casos, subproductos de industrias agroalimentarias o metalúrgicas.La tesis consta de diferentes capítulos enmarcados en tres secciones: (i) Eliminación de cromo hexavalente y trivalente (ii) Eliminación de cationes divalentes de metales pesados en presencia de complejantes y en mezclas multimetálicas y (iii) Eliminación de arsénico utilizando un subproducto de la industria de cromados metálicos como adsorbente. Los resultados obtenidos ponen de manifiesto que ciertos residuos industriales pueden ser utilizados como adsorbentes en la detoxificación de efluentes contaminados con metales pesados. La tecnología propuesta representa una alternativa sostenible y de bajo coste frente a los tratamientos actuales más costosos y dependientes, en muchas ocasiones, de productos derivados del petróleo.

Impact of chlorophenols and heavy metals on soil microbiota: their effects on activity and community composition, and resistant strains with potential for bioremetiation

Pollution by toxic compounds is one of the most relevant environmental damages to ecosystems produced by human activity and, therefore, it must be considered in environmental protection and restoration of contaminated sites. According to this purposes, the main goal of this doctoral thesis has been to analyse the impact of several chlorophenols and heavy metals on the microbial communities of two typical Mediterranean soils. The ecological risk concentrations of each pollutant, which have been determined according to respirometric activity and changes in the microbial community composition, and the factors that influence on their effective toxic concentrations (bioavailable pollutants) have been analysed in order to predict their potential impact on different soil ecosystems and provide scientific data for the regulation of the soil protection policies. Moreover, resistant microorganisms with pollutant removal capacities have been isolated from artificially contaminated soil microcosms and tested in axenic cultures, to infer their potential usefulness for bioremediation.

Isomerism and C-H, C-C, O-O, C-O bond activation studies by transition metals

Aquesta tesi és el reflex que de la cooperació entre grups experimentals i grups teòrics s'aconsegueix l'assoliment d'objectius inassolibles de forma individual. A partir de la DFT s'expliquen processos inorgànics i organometàl·lics de gran valor biològic i/o industrial. La tesi està enfocada especialment a l'estudi de complexos mononuclears i binuclears de coure, on té lloc l'activació d'enllaços C-H, C-C, i O-O. L'estudi de complexos octaèdrics de ruteni ha permès dur a terme extensos estudis isomèrics i racionalitzar les propietats espectroscòpiques dels mateixos. A més a més, estudis més puntuals respecte clusters de coure, l'estudi de la reacció de Pawson-Khand, l'estudi d'enllaços Pt-Pt en complexos trimèrics de platí, a més a més de l'estudi de la isomeria de complexos de Ni i Pt.

Theoretical studies of systems of biochemical interest containing Fe and Cu transition metals

La presència de la química teòrica i computacional està augmentant en quasi tots els camps de la recerca en química. Els càlculs teòrics poden ajudar a entendre millor l'estructura, les propietats i la reactivitat de compostos metàl·lics d'àrees tan diferents com la química inorgànica, organometàl·lica i bioinorgànica. No obstant això, és imprescindible utilitzar la metodologia adequada per obtenir resultats teòrics fiables. Els estudis d'aquesta tesi es poden dividir en dos grups diferents. El primer grup inclou l'estudi teòric del mecanisme de reacció de diversos sistemes que contenen coure i tenen diferents estructures Cun-O2. Aquests estudies s'han dut a terme amb l'objectiu de profunditzar en la natura dels processos oxidants químics i biològics promoguts per sistemes que contenen coure. En la segona part de la tesi, s'estudia la fiabilitat de diferents tècniques utilitzades per estudiar l'estructura electrònica i la reactivitat de sistemes que contenen coure, ferro i altres metalls de transició.

Simulating metals and mine discharges in river basins using a new integrated catchment model for metals: pollution impacts and restoration strategies in the Aries-Mures river system in Transylvania, Romania

The INtegrated CAtchment (INCA) model has been developed to simulate the impact of mine discharges on river systems. The model accounts for the key kinetic chemical processes operating as well as the dilution, mixing and redistribution of pollutants in rivers downstream of mine discharges or acid rock drainage sites. The model is dynamic and simulates the day-to-day behaviour of hydrology and eight metals (cadmium, mercury, copper, zinc, lead, arsenic, manganese and chromium) as well as cyanide and ammonia. The model is semi-distributed and can simulate catchments, sub-catchment and in-stream river behaviour. The model has been applied to the Roia Montan Mine in Transylvania, Romania, and used to assess the impacts of old mine adits on the local catchments as well as on the downstream Aries and Mures river system. The question of mine restoration is investigated and a set of clean-up scenarios investigated. It is shown that the planned restoration will generate a much improved water quality from the mine and also alleviate the metal pollution of the river system.

The effect of organic materials on the mobility and toxicity of metals in contaminated soils

Organic materials such as compost are often proposed as suitable materials for the remediation of contaminated brownfield sites intended for soft end-use. In addition to vitalising the soil, they are also believed to immobilise metals thereby breaking contaminant-receptor pathways and reducing the ecotoxicity of the contaminants. However, some research has demonstrated contradictory effects between composts on metal immobilisation. In the present study, four different composts and a liming product containing organic matter (LimeX70) were tested to examine both their metal retention and toxicity reduction capabilities on three different metal contaminated soils. Leaching tests, a plant growth test with Greek cress (Lepidium sativum), an earthworm (Eisenia fetida) survival and condition test and a bacterial toxicity test using Vibrio fischeri were carried out. The leaching test results showed that spent mushroom compost caused an increase in metal concentration in the leachates, while LimeX70 caused a decrease. The variation in behaviour between different amendments for each soil was high, so a generic conclusion could not be drawn. Toxicity tests showed significant reduction of metal bioavailability and toxicity for Greek cress, earthworms and bacteria. The results also suggest that more research should be undertaken to understand the mechanisms involved in metal complexation using different types of organic matter, in order to optimise the use of organic materials like compost for soil remediation. Crown Copyright (C) 2007 Published by Elsevier Ltd. All rights reserved.

Reduction of arsenic uptake by lettuce with ferrous sulfate applied to contaminated soil

Soil contamination by arsenic (As) presents a hazard in many countries and there is a need for techniques to minimize As uptake by plants. A proposed in situ remediation method was tested by growing lettuce (Lactuca sativa L. cv. Kermit) in a greenhouse pot experiment on soil that contained 577 mg As kg(-1), taken from a former As smelter site. All combinations of iron (Fe) oxides, at concentrations of 0.00, 0.22, 0.54, and 1.09% (w/w), and lime, at concentrations of 0.00, 0.27, 0.68, and 1.36% (w/w), were tested in a factorial design. To create the treatments, field-moist soil, commercial-grade FeSO4, and ground agricultural lime were mixed and stored for one week, allowing Fe oxides to precipitate. Iron oxides gave highly significant (P < 0.001) reductions in lettuce As concentrations, down to 11% of the lettuce As concentration for untreated soil. For the Fe oxides and lime treatment combinations where soil pH was maintained nearly constant, the lettuce As concentration declined in an exponential relationship with increasing FeSO4 application rate and lettuce yield was almost unchanged. Iron oxides applied at a concentration of 1.09% did not give significantly lower lettuce As concentrations than the 0.54% treatment. Simultaneous addition of lime with FeSO4 was essential. Ferrous sulfate with insufficient lime lowered soil pH and caused mobilization of Al, Ba, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Sr, and Zn. At the highest Fe oxide to lime ratios, Mn toxicity caused severe yield loss.

Influence of dissolved organic matter on the solubility of heavy metals in sewage-sludge-amended soils

Sewage-sludge-amended soils generally contain elevated levels of organic matter and heavy metals compared to control soils. Because organic matter is known to complex with heavy metals, the solubility behavior of the organic matter in such soils may exert a significant influence on the solubility of the metals. Little is known about such a process. Using batch experiments in which the solubility of organic matter in a heavily sludge-amended soil was artificially manipulated, we show that the solubilities of the heavy metals copper (Cu), nickel (Ni), and lead (Pb) show a strong positive relationship to the solubility of organic matter, particularly at high pH. The results suggest that under field conditions, spatiotemporal variations in the solid-solution partitioning of organic matter may have a bearing on the environmental significance (mobility and bioavailability) of these heavy metals.

Distribution of selected heavy metals in sediments of the Agueda river (Central Portugal)

The state of river water deterioration in the Agueda hydrographic basin, mostly in the western part, partly reflects the high rate of housing and industrial development in this area in recent years. The streams have acted as a sink for organic and inorganic loads from several origins: domestic and industrial sewage and agricultural waste. The contents of the heavy metals Cr, Cd, Ni, Cu, Pb, and Zn were studied by sequential chemical extraction of the principal geochemical phases of streambed sediments, in the <63 mum fraction, in order to assess their potential availability to the environment, investigating, the metal concentrations, assemblages, and trends. The granulometric and mineralogical characteristics of this sediment fraction were also studied. This study revealed clear pollution by Cr, Cd, Ni, Cu, Zn, and Pb, as a result from both natural and anthropogenic origins. The chemical transport of metals appears to be essentially by the following geochemical phases, in decreasing order of significance: (exchangeable + carbonates) much greater than (organics) much greater than (Mn and Fe oxides and hydroxides). The (exchangeable + carbonate) phase plays an important part in the fixation of Cu, Ni, Zn, and Cd. The organic phase is important in the fixation of Cr, Pb, and also Cu and Ni. Analyzing the metal contents in the residual fraction, we conclude that Zn and Cd are the most mobile, and Cr and Pb are less mobile than Cu and Ni. The proximity of the pollutant sources and the timing of the influx of contaminated material control the distribution of the contaminant-related sediments locally and on the network scale.