Synthesis, characterization and reactivity of new cobalt, palladium and nickel complexes bearing α-diimines and P, O ligands

This work describes the synthesis and characterization of a series of new α-diimine and P,O, β-keto and acetamide phosphines ligands, and their complexation to Ni(II), Co(II),Co(III) and Pd(II) to obtain a series of new compounds aiming to study their structural characteristics and to test their catalytic activity. All the compounds synthesized were characterized by the usual spectroscopic and spectrometric techniques: Elemental Analysis, MALDI-TOF-MS spectrometry, IR, UV-vis, 1H, 13C and 31P NMR spectroscopies. Some of the paramagnetic compounds were also characterized by EPR. For the majority of the compounds it was possible to solve their solid state structure by single crystal X-ray diffraction. Tests for olefin polymerization were performed in order to determine the catalytic activity of the Co(II) complexes. Chapter I presents a brief introduction to homogenous catalysis, highlighting the reactions catalyzed by the type of compounds described in this thesis, namely olefin polymerization and oligomerization and reactions catalyzed by the complexes bearing α-diimines and P,O type ligands. Chapter II is dedicated to the description of the synthesis of new α-diimines cobalt (II) complexes, of general formula [CoX2(α-diimine)], where X = Cl or I and the α-diimines are bis(aryl)acenaphthenequinonediimine) (Ar-BIAN) and 1,4-diaryl-2,3-dimethyl-1,4-diaza-1,3-butadiene (Ar-DAB). Structures solved by single crystal X-ray diffraction were obtained for all the described complexes. For some of the compounds, X-band EPR measurements were performed on polycrystalline samples, showing a high-spin Co(II) (S = 3/2) ion, in a distorted axial environment. EPR single crystal experiments on two of the compounds allowed us to determine the g tensor orientation in the molecular structure. In Chapter III we continue with the synthesis and characterization of more cobalt (II)complexes bearing α-diimines of general formula [CoX2(α-diimine)], with X = Cl or I and α-diimines are bis(aryl)acenaphthenequinonediimine) (Ar-BIAN) and 1,4-diaryl-2,3-dimethyl- 1,4-diaza-1,3-butadiene (Ar-DAB). The structures of three of the new compounds synthesized were determined by single crystal X-ray diffraction. A NMR paramagnetic characterization of all the compounds described is presented. Ethylene polymerization tests were done to determine the catalytic activity of several of the Co(II) complexes described in Chapter II and III and their results are shown. In Chapter IV a new rigid bidentate ligand, bis(1-naphthylimino)acenaphthene, and its complexes with Zn(II) and Pd(II), were synthesized. Both the ligand and its complexes show syn and anti isomers. Structures of the ligand and the anti isomer of the Pd(II) complex were solved by single crystal X-ray diffraction. All the compounds were characterized by elemental analysis, MALDI-TOF-MS spectrometry, and by IR, UV-vis, 1H, 13C, 1H-1H COSY, 1H-13C HSQC, 1H-13C HSQC-TOCSY and 1H-1H NOESY NMR when necessary. DFT studies showed that both conformers of [PdCl2(BIAN)] are isoenergetics and can be obtain experimentally. However, we can predict that the isomerization process is not available in square-planar complex, but is possible for the free ligand. The molecular geometry is very similar in both isomers, and only different orientations for naphthyl groups can be expected. Chapter V describes the synthesis of new P, O type ligands, β-keto phosphine, R2PCH2C(O)Ph, and acetamide phosphine R2PNHC(O)Me, as well as a series of new cobalt(III) complexes namely [(η5-C5H5)CoI2{Ph2PCH2C(O)Ph}], and [(η5- C5H5)CoI2{Ph2PNHC(O)Me}]. Treating these Co(III) compounds with an excess of Et3N, resulted in complexes η2-phosphinoenolate [(η5-C5H5)CoI{Ph2PCH…C(…O)Ph}] and η2- acetamide phosphine [(η5-C5H5)CoI{Ph2PN…C(…O)Me}]. Nickel (II) complexes were also obtained: cis-[Ni(Ph2PN…C(…O)Me)2] and cis-[Ni((i-Pr)2PN…C(…O)Me)2]. Their geometry and isomerism were discussed. Seven structures of the compounds described in this chapter were determined by single crystal X-ray diffraction. The general conclusions of this work can be found in Chapter VI.

On-line system for faults detection in induction motors based on PCA

Dissertation to obtain the degree of Master in Electrical and Computer Engineering

Constraint solving over multi-valued logics - application to digital circuits

Due to usage conditions, hazardous environments or intentional causes, physical and virtual systems are subject to faults in their components, which may affect their overall behaviour. In a ‘black-box’ agent modelled by a set of propositional logic rules, in which just a subset of components is externally visible, such faults may only be recognised by examining some output function of the agent. A (fault-free) model of the agent’s system provides the expected output given some input. If the real output differs from that predicted output, then the system is faulty. However, some faults may only become apparent in the system output when appropriate inputs are given. A number of problems regarding both testing and diagnosis thus arise, such as testing a fault, testing the whole system, finding possible faults and differentiating them to locate the correct one. The corresponding optimisation problems of finding solutions that require minimum resources are also very relevant in industry, as is minimal diagnosis. In this dissertation we use a well established set of benchmark circuits to address such diagnostic related problems and propose and develop models with different logics that we formalise and generalise as much as possible. We also prove that all techniques generalise to agents and to multiple faults. The developed multi-valued logics extend the usual Boolean logic (suitable for faultfree models) by encoding values with some dependency (usually on faults). Such logics thus allow modelling an arbitrary number of diagnostic theories. Each problem is subsequently solved with CLP solvers that we implement and discuss, together with a new efficient search technique that we present. We compare our results with other approaches such as SAT (that require substantial duplication of circuits), showing the effectiveness of constraints over multi-valued logics, and also the adequacy of a general set constraint solver (with special inferences over set functions such as cardinality) on other problems. In addition, for an optimisation problem, we integrate local search with a constructive approach (branch-and-bound) using a variety of logics to improve an existing efficient tool based on SAT and ILP.

Evolução tectónica mesozóica da Bacia Lusitaniana

The evolution of the Lusitanian Basin, localized on the western Iberian margin, is closely associated with the first opening phases of the North Atlantic. It persisted from the Late Triassic to the Early Cretaceous, more precisely until the end of the Early Aptian, and its evolution was conditioned by inherited structures from the variscan basement. The part played by the faults that establish its boundaries, as regards the geometric and kinematic evolution and the organization of the sedimentary bodies, is discussed here, as well as with respect to important faults transversal to the Basin. A basin evolution model is proposed consisting of four rifting episodes which show: i) periods of symmetrical (horst and graben organization) and asymmetrical (half graben organization) geometric evolution; ii) diachronous fracturing; iii) rotation of the main extensional direction; iv) rooting in the variscan basement of the main faults of the basin (predominantly thick skinned style). The analysis and regional comparison, particularly with the Algarve Basin, of the time intervals represented by important basin scale hiatuses near to the renovation of the rifting episodes, have led to assume the occurrence of early tectonic inversions (Callovian–Oxfordian and Tithonian–Berriasian). The latter, however, had a subsequent evolution distinct from the first: there is no subsidence renovation, which is discussed here, and it is related to a magmatic event. Although the Lusitanian Basin is located on a rift margin which is considered non-volcanic, the three magmatic cycles as defined by many authors, particularly the second (approx. 130 to 110 My ?), performed a fundamental part in the mobilization of the Hettangian evaporites, resulting in the main diapiric events of the Lusitanian Basin. The manner and time in which the basin definitely ends its evolution (Early Aptian) is discussed here. Comparisons are established with other west Iberian margin basins and with Newfoundland basins. A model of oceanization of this area of the North Atlantic is also presented, consisting of two events separated by approximately 10 My, and of distinct areas separated by the Nazaré fault. The elaboration of this synthesis was based on: - information contained in previously published papers (1990 – 2000); - field-work carried out over the last years, the results of which have not yet been published; - information gathered from the reinterpretation of geological mapping and geophysical (seismic and well logs) elements, and from generic literature concerning the Mesozoic of the west iberian margin.

Contributions à la Paléontologie du Miocène moyen continental du Bassin du Tage. III - Mammifères - Póvoa de Santarém, Pêro Filho et Chões (Secorio). Conclusions générales

This study on middle Miocene mammalian faunas from Tagus'basin deals particularly with some small mammals hitherto undescribed from Portugal, including a new Glirid (Paraglirulus scalabicensis nov. sp.); it allows an accurate datation by biostratigraphical standards, Megacricetodon crusafonti, Fahlbuschia darocensis, Cricetodon jotae being characteristic of mammalian MN6 unit, thus their age is nearly that of Sansan and Manchones (however the presence of Peridyromys hamadryas and Lagopsis verus do suggest, amidst this biozone, a somewhat later age than Sansan's); it contributes with indirect correlation data with marine formations, as underlying oyster-bearing beds most probably are in correspondance to the apogee of the same transgression that deposed near Lisbon ”schlier" facies from VI-a division (Serravalian, Blow's zones 10-13, Globorotalia meyeri zone); the diversity of mammalian assemblages is surely related to an environement with varied biotopes, whose characterisation becomes easier if account is taken of the preceding papers on mollusks (G. Truc) and Cyprinid fishes (J. Gaudant), and also according to some unpublished paleobotanical data (J. Pais). A table with a synthesis of all paleontological data so far known is presented.

Cheirogaster sp. (O. Testudines, Fam. Testudinidae, Geochelone sl.) du Paléogène de Naia, Tondela et l’âge du gisement

A land tortoise from a new locality at Naia, Tondela, is described. It is to be reported either to an advanced form of the genus Hadrianus or to an archaic representative of Cheirogaster; it may be included in the comprehensive genus Geochelone s.l., excluding however Ergilemys and its descendants. There is a strong possibility in favour of Cheirogaster. Testudo must also be excluded. It is not possible to classify this specimen at species'level. Our specimen does agree best with Upper Eocene Testudinidae and with some Lower Oligocene ones. Its age is certainly not Upper Oligocene or later, nor Lower and Middle Eocene. This datation is not opposed to the age of the fossiliferous clays of Naia as supposed by correlation with another locality - Côja, about 30 km to the South - which yielded an assemblage of mammals whose Ludian (Upper Bartonian s.l.) age seems well established. Naia and Côja's fossil-bearing clays must be nearly synchronous; their origin is well in place among the phenomena related to the surrection of iberian Central Chain during paroxysmal phase of pyrenean orogenesis.

A reconnaissance study of Upper Jurassic sediments of the Lusitanian Basin

The Upper Jurassic evolution of the Lusitanian Basin is shown to be linked to the rifting phase which preceded the separation of Iberia and the Grand Banks. Structural controls on sedimentation include both NNE-SSW trending faults in the Hercynian basement, and contemporaneous movement of salt diapirs. At the beginning of Upper Oxfordian times, the entire basin had been levelled to within a few metres of sea level, so that the freshwater algal marsh and marginal marine facies of the Cabaços and Vale Verde Beds rest on Triassic to Callovian strata. In the latter part of the Upper Oxfordian. carbonate sedimentation continued, with fluctuating salinity lagoons in the north (Pholodomya protei Beds) separated from shallow open marine carbonates in the south (Montejunto Beds) by the Caldas da Rainha diapir-barrier island complex. The commencement of rifting is recorded in the Kimmeridgian by the sudden influx of terrigenous clastics (developed in both fluviatile and deltaic/submarine fan environments) and accelerated depositional rates in excess of 10cm/10 k.yrs in association with contemporaneous faulting along the SE margin of the Arruda sub-basin. The Caldas-Santa Cruz chain of diapiric structures continued to influence the distribution of carbonate and clastic sediments. In the Portlandian, a simpler facies pattern occurs, with fluviatile clastics interfingering to the south with shallow low energy carbonates.

Vertébrés du Miocène moyen de Amor (Leiria) - importance stratigraphique

Some outcrops in the western part of Leiria's diapir yielded continental fossils in five points near Amor village (mammals, other vertebrata, and gastropoda). This is most significant as it is the first locality where miocene age could undoubtedly been ascribed to formations northwards the Iberian Central Chain and Nazare's accident. Mammalian fauna comprises 18 taxa. A new cricetid species, Fahlbuschia freudenthali n. sp. is described. This fauna allows to date fossil-bearing units from Upper Orleanian, MN5 mammal zone, that may be correlated to Upper Langhian marine stage. As the fauna is quite varied, it is possible to recognize the main characters of environment and of climatic conditions. It may probably be assumed that at the time the climate was of mediterranean type, generally warmer than today.

Evolução paleogeográfica e paleobiogeográfica do Caloviano-Kimeridgiano do Algarve

The littoral and the «barrocal» of the Algarve correspond in part to a meso-cenozoic sedimentary basin with a deeping south monocline structure, cut by North-South faults and by two East-West longitudinal flexures. The lithostratigraphic and chronostratigraphic study of the Jurassic formations, undertaken during the last years, allow a better knowledge of the paleogeographic and paleobiogeographic evolution of these formations and particularly of the Callovian-Kimmeridgian. Lower Callovian facies, being similar from Sagres in the West to beyond Tavira, show the uniformity of the sedimentary conditions. Since Middle Callovian, the beginning of the regressive cycle is responsible for a major unconformity between Dogger and Malm. During the Lower Oxfordian a new sedimentary cycle begins with a transgression afecting the region south of the Albufeira-São Brás de Alportel-Tavira line thus originating a gulf centered in the Loulé area which rapidly diminishes since the Lower Kimmeridgian. The faunistic affinities are always tipically tethyan although some classic boreal fauna exist, in contrast with the Northern Tagus basin (where affinities are sub-boreal during the Callovian).

Stratigraphie du Dogger et crise lusitanienne dans la Serra de Candeeiros

New elements about the stratigraphy of the Serra de Candeeiros Dogger and Lower «Lusitanian» are presented. The Lower Aalenian was recognized for the first time. Bathonian (more than 50 metres thick) is dated on brachiopods and foraminifera. It corresponds to a series of massive micritic, biodetritical, coral-reef, chaetetid, bryozoa and oolitic-limestones. Callovian (120 m) begins by whitish or yellowish limestones with ammonites and brachiopods of the Gracilis zone. It is followed by regressive limestone sequences ending with thick oncolitic layers. The «Lusitanian» base is formed by greyish lagoon brackish limestones; it lies unconformably on the Dogger, with or without angular and/or cartographic unconformity. This radical facies change is related to tectonic deformation of several blocks between the Nazaré and Tagus faults during Oxfordian times.

A high level e-maintenance architecture to support on-site teams

Emergent architectures and paradigms targeting reconfigurable manufacturing systems increasingly rely on intelligent modules to maximize the robustness and responsiveness of modern installations. Although intelligent behaviour significantly minimizes the occurrence of faults and breakdowns it does not exclude them nor can prevent equipment’s normal wear. Adequate maintenance is fundamental to extend equipments’ life cycle. It is of major importance the ability of each intelligent device to take an active role in maintenance support. Further this paradigm shift towards “embedded intelligence”, supported by cross platform technologies, induces relevant organizational and functional changes on local maintenance teams. On the one hand, the possibility of outsourcing maintenance activities, with the warranty of a timely response, through the use of pervasive networking technologies and, on the other hand, the optimization of local maintenance staff are some examples of how IT is changing the scenario in maintenance. The concept of e-maintenance is, in this context, emerging as a new discipline with defined socio-economic challenges. This paper proposes a high level maintenance architecture supporting maintenance teams’ management and offering contextualized operational support. All the functionalities hosted by the architecture are offered to the remaining system as network services. Any intelligent module, implementing the services’ interface, can report diagnostic, prognostic and maintenance recommendations that enable the core of the platform to decide on the best course of action.

Water treatments in semi-closed cooling circuits and their impact on the quality of effluents discharged by CERN

Dissertação apresentada à Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em Engenharia do Ambiente, Gestão de Sistemas Ambientais

Orchestration of heterogeneous middleware services and its application to a comand and control platform

MSC Dissertation in Computer Engineering

Water treatments in semi-closed cooling circuits and their impact on the quality of effluents discharged by CERN

Mestrado integrado em Engenharia do Ambiente, perfil: Gestão de Sistemas Ambientais

Learning with tangible interfaces

Trabalho apresentado no âmbito do Mestrado em Engenharia Informática, como requisito parcial para obtenção do grau de Mestre em Engenharia Informática