In der vorliegenden Arbeit wurde die Phasenbildung im ternären System Ni(OH)2-NiCl2-H2O systematisch untersucht. Die basischen Nickel(II)-chlorid Phasen NiCl(OH), Ni2Cl(OH)3, NiClx(OH)2-x, Ni3Cl2+x(OH)4-x ∙ 2 H2O mit x = 0,26; 0,48; 0,82 und Ni3Cl2+x(OH)4-x ∙ 4 H2O mit x = 0,10 konnten phasenrein hergestellt und deren Kristallstrukturen mittels hochauflösender Röntgenpulverdiffraktometrie aufgeklärt werden. Die so erhaltenen strukturellen Daten wurden durch Anwendung von IR-und Spektroskopie, UV/VIS-Spektroskopie, SQUID-Messungen, Thermoanalysen und temperaturaufgelöster in-situ Röntgenpulverdiffraktometrie als komplementäre Methoden bestätigt. Weiterhin konnte eine allgemein anwendbare Routine zur Beschreibung der Diffraktionseffekte stapelfehlerbehafteter Schichtverbindungen für das Programm TOPAS entwickelt werden. Die Bildung und Stabilität der basischen Nickel(II)-chlorid Phasen in wässriger Nickel(II)-chlorid Lösung wurde systematisch bei 200°C und 25°C über Zeiträume von zwei Jahren untersucht und Löslichkeitsdaten ermittelt. Des Weiteren erfolgte die Untersuchung der Wechselwirkung von Magnesium Oxid und basischen Magnesiumchlorid Phasen mit wässrigen nickelhaltigen Magnesiumchlorid Lösungen. Hierbei konnte die Mischkristallbildung zwischen analogen basischen Magnesium- und Nickel(II)-chloridphasen beobachtet werden. Es wurde festgestellt, dass basische Magnesiumchloride und Magnesiumoxid ein gutes Rückhaltevermögen für gelöstes Nickel aufweisen und dass ein Zutritt von gelöstem Nickel weder die Pufferwirkung noch die Beständigkeit der basischen Magnesiumchlorid Phasen beeinträchtigt.

Histidinkinase-Rhodopsine (HKRs) können als besondere Gruppe der Hybrid-Histidinkinasen beschrieben werden, deren N-terminale sensorische Domäne ein mikrobielles Rhodopsin ist. HKR-codierende Sequenzen konnten in den Genomen verschiedener Algen, Pilze und Amoeben gefunden werden doch ihre Aufgaben und Wirkungsweisen sind bisher ungeklärt. Im Rahmen dieser Arbeit wurden die rekombinanten Rhodopsin-Domänen von zwei HKRs mit verschiedenen spektroskopischen Techniken charakterisiert. Sie zeigten mehrere Besonderheiten. Das Rhodopsin-Fragment von Cr-HKR1 aus Chlamydomonas reinhardtii kann durch alternierende kurzwellige und langwellige Belichtung zwischen zwei stabilen Absorptionsformen konvertiert werden: einer Blaulicht-absorbierenden (Rh-Bl) und einer UVA-Licht-absorbierenden Form (Rh-UV). Dies resultiert aus der ungewöhnlichen thermischen Stabilität des Zustandes mit deprotonierter Schiff’scher Base. Das zweite charakterisierte HKR, die Os-HKR-Rhodopsin-Domäne aus der marinen Picoalge Ostreococcus tauri, zeigt eine Dunkelabsorption von 505 nm. Auch Os-HKR ist photochrom und die deprotonierte Spezies kann effizient akkumuliert werden. Diese P400-Absorptionsform ist jedoch nicht völlig stabil sondern es kommt nach Belichtungsende zur langsamen Dunkelzustands-Regeneration. Überraschenderweise konnte die Bindung sowie die transiente Abgabe eines Anions während des Os-HKR-Photozyklus festgestellt werden. Somit beeinflusst nicht nur das Licht, sondern auch das Salz in der Umgebung die Os-HKR-Reaktionen. Aufgrund ihrer photochromen Eigenschaften werden die HKRs als wirksame lichtinduzierte Schalter für die C-terminalen Signaltransduktionsdomänen postuliert. Schwingungsspektroskopische Analysen deckten eine Heterogenität hinsichtlich der im Protein gebundenen Retinal‐Konfiguration sowie die Existenz von zwei parallelen Photozyklen auf. Jeder dieser Photozyklen geht aus einer der beiden Retinal-Isomere hervor. / Histidine kinase rhodopsins (HKRs) can be described as hybrid histidine kinases with a microbial rhodopsin as N-terminal sensory domain. HKR-encoding sequences were found in the genomes of various unicellular organisms such as algae, fungi and amoeba but their mechanistic and physiologic function is unknown. During this work the absorptive properties of the recombinant rhodopsin domains of two HKRs were studied by the usage of different spectroscopic techniques. Both HKRs showed unusual characteristics. The rhodopsin fragment of Cr‐HKR1 from Chlamydomonas reinhardtii can be interconverted between two stable absorbance forms by the alternate application of short‐ and long‐wavelength light: a blue light-absorbing dark form (Rh-Bl) and a UVA light-absorbing form (Rh-UV). This unusual photocycle results from the uncommon thermal stability of the absorbance state with a deprotonated retinal Schiff base. The second studied HKR, the Os‐HKR rhodopsin domain from the marine picoalga Ostreococcus tauri, shows an absorbance maximum at 505 nm in darkness. Likewise Cr‐HKR1 the Os‐HKR is photochromic and the deprotonated form P400 can be efficiently accumulated. But the Os-HKR P400-form is not completely stable. A slow dark state recovery occurs. Surprisingly the dark state absorbance of Os‐HKR was found to be dependent on anion binding in the protein. Furthermore during the photocycle the transient anion release occurs and therefore not only light but also salt impacts the Os-HKR-reactions. Due to their pronounced photochromic properties, the HKRs are postulated to act as effective molecular switches for the C-terminal signal transduction domains in response to the light conditions. Vibrational spectroscopy revealed the heterogeneity with regard to the retinal configuration bound in the HKRs suggesting the existence of two parallel photocycles. Either of these photocycles originates from one of the two retinal isoforms.

This doctoral thesis consists of a literature review, presented in two papers, and another six papers describing experimental studies of the influence of different kinds of wax and polyphosporic acid on bitumen and asphalt concrete mixture properties. The literature review should give an extensive description of the field of knowledge concerning wax in bitumen. Effects of wax in crude oil, bitumen and asphalt concrete as well as test methods for studying these effects are described. Theories behind possible mechanisms are also discussed, and commercial wax as additive to bitumen for different purposes included. The experimental parts comprise laboratory studies involving totally five 160/220 penetration base bitumens from different sources, two isolated bitumen waxes, five commercial waxes and one polyphosphoric acid. Asphalt concrete slabs, containing base or modified bitumen were prepared and tested. Binder properties were evaluated using different types of laboratory equipment, such as dynamic shear rheometer (DSR), bending beam rheometer (BBR), differential scanning calorimeter (DSC), force ductilometer, as well as equipment for determining conventional parameters like penetration, softening point, viscosity, and Fraass breaking point. Fourier Transform Infrared (FTIR) spectroscopy and Thin Layer Chromatography (TLC-FID) were used for chemical characterization. The binders were aged by means of the rolling thin film oven test (RTFOT) and pressure ageing vessel (PAV) in combination. Asphalt concrete properties were evaluated at low temperatures using the tensile strain restrained specimen test (TSRST) and creep test at -25°C. Dynamic creep testing was performed at 40°C, as well as complex modulus tests between 0 and 20°C. Binder test results indicated that the magnitude and type of effect on bitumen rheology depend on the bitumen itself, type of crystallizing fraction in the bitumen and/or type and amount of additive used. Bitumen composition was found to be of decisive importance. Adding polyethylene wax or polyphosphoric acid, especially to a non-waxy 160/220 penetration grade bitumen, showed no or positive effects on the rheological behaviour at low temperatures (decrease in stiffness) as well as medium and high temperatures (increase in complex modulus and decrease in phase angle). However, the corresponding positive effects could not be shown in dynamic creep testing (at 40°C) of asphalt concrete mixtures containing these modified binders. Adding FT-paraffin decreased the physical hardening index for all bitumens. Also polyethylene wax and montan wax showed this effect for some bitumens. Slack wax showed a large increasing effect on physical hardening, and polyphosphoric acid none or a minor negative effect. No correlation between physical hardening index (PHI) and wax content by DSC was found in this study, involving both natural bitumen wax and commercial wax. Addition of the commercial waxes used showed no or marginally positive influence on bitumen ageing properties for the bitumens and test conditions used. Comparing asphalt mixture test results to the corresponding binder test results, the effects on asphalt mixtures from adding commercial wax or polyphosphoric acid were less evident. Significant binder physical hardening by BBR could not be confirmed by TSRST. / QC 20101006

Im Rahmen der vorliegenden Arbeit werden die Synthese und Charakterisierung eines thermisch-kontrollierten und eines photochemisch-kontrollierten reversiblen Polymersystems vorgestellt. Weiterhin werden Poly(dimethyl)siloxan-Oberflächen mit Amino-, Isocyanat-, Furan-, Maleimid- und Cumarin-Gruppen funktionalisiert. Hierbei werden sowohl bekannte als auch neuartige Wege der Oberflächenmodifizierung vergleichend untersucht und bewertet. Ausgehend von den hergestellten Cumarin-funktionalisierten Poly(dimethyl)siloxan-Oberflächen wird eine Anbindung des synthetisierten photochemisch-kontrollierten reversiblen Polymersystems an diese Oberflächen untersucht. Des Weiteren wird die Anbindung des synthetisierten thermisch kontrollierten reversiblen Polymersystems sowohl an den hergestellten Maleimid- als auch an den Furan-funktionalisierten Poly(dimethyl)siloxan-Oberflächen analysiert. Basierend auf den vorgestellten Cumarin-Funktionalisierungen werden photoaktive Oberflächen beschrieben und mittels ATR-IR-spektroskopischer und UV/Vis-spektroskopischer Methoden analysiert.

It is known that boron containing compounds exhibit interesting chemical and physical properties. In the past 50 years modern preparative methods have led to an overwhelming number of different structures of novel and often unexpected boron–sulfur and boron–selenium compounds. Among all these new compounds, there was only one which comprises rare earth metal (RE), boron and heavier chalcogen, namely sulfur, the europium thioborate Eu[B2S4] [1]. Selenoborates of rare earth metals are hitherto unknown. On the other hand, rare earth oxoborates represent a well-known class of compounds [2] with a wide range of applications, especially in the field of optical materials. In addition, well-defined boron compounds containing the heavier group 16 elements are fairly difficult to prepare due to the high reactivity of in situ formed boron chalcogenides towards most container materials at elevated temperatures. The chalcogenoborates of the heavier chalcogens are sensitive against oxidation and hydrolysis and therefore have to be handled in an inert environment. Therefore, developing and optimization of preparative routes for the syntheses of pure and crystalline RE thio- and selenoborates was needed. In the course of this study, the application of different preparation routes, such as optimized high-temperature routes (HT), metathesis reactions and high-pressure high-temperature routes (Hp – HT), led to sixteen new rare earth thioborates. Their crystal structures were solved and/or refined from powder and single crystal X-ray diffraction data, while the local structure around rare earth metal was confirmed from the results of the EXAFS analyses. Quantum mechanical calculations were used within this work in order to investigate the arrangement of intrinsic vacancies on the boron sites in the crystal structures of rare earth thioborates. Thermal, magnetic and optical properties of these compounds are also discussed. The rare earth thioborates discovered during this work are the first examples of ternary thioborates containing trivalent cations. These compounds can be divided into two groups of isotypic compounds: the rare earth orthothioborates with general formula REIII[BS3] (RE = La – Nd, Sm, Gd and Tb) [3] and the rare earth thioborate sulfides with general formula REIII¦9B5S21, (RE = Gd – Lu, and Y) [4]. In the crystal structure of RE[BS3] (orthorhombic, space group Pna21, Z = 4), the sulfur atoms form the vertices of corrugated kagome nets, within which every second triangle is occupied by boron and the large hexagons are centered by RE cations. The structural features of the isotypic RE[BS3] phases show great similarities to those of rare earth oxoborates RE[BO3] and orthothioborates of alkali and alkaline earth metals as well as to thallium orthothioborate, yet pronounced differences are also observed: the [BS3]3– groups in the crystal structures of RE[BS3] are more distorted, where the distortion decreases with the decreasing size of the RE element, and the coordination environments of the [BS3]3– groups in the crystal structures of RE[BS3] are different in comparison with the coordination environments of the [BO3]3– groups in the crystal structures of λ-Nd[BO3] [5] and of o-Ce[BO3] [6]. The results of the IR and Raman investigations are in agreement with the presence of [BS3]3– anions in the crystal structure of RE[BS3]. Thermal analyses revealed the thermal stability of these compounds under inert conditions up to ~ 1200 K. Analyses of the magnetic properties of the Sm, Gd and Tb thioborates showed that both Gd and Tb phases order antiferromagnetically. The magnetic susceptibility for Sm orthothioborate approximately follows the Van-Vleck theory for Sm3+. Between 50 K and 62 K a transition appears which is independent of the magnetic field: the magnetic susceptibility becomes lower. This effect might indicate a discontinuous valence transition of Sm which was further investigated by means of XANES and X-ray diffraction using synchrotron radiation, both at low temperatures. The series of isotypic RE thioborate sulfides with composition RE9B5S21, was obtained by the application of Hp – HT conditions to starting mixtures with the initial chemical composition “REB3S6“, after careful optimization of the pressure, temperature and treatment time, as well as the composition of the starting mixtures. Their crystal structures adopt the Ce6Al3.33S14 [7] structure type (hexagonal, space group P63, Z = 2/3). The special features of the RE9B5S21 crystal structures, concerning boron site occupancies and different coordination environments of the two crystallographically independent boron sites, were investigated in more detail by means of quantum chemical calculations, electron diffraction methods, optical and X-ray absorption spectroscopy as well as by 11B NMR spectroscopy. The results obtained from these different experimental and computational methods are in good mutual agreement. The crystal structures of the RE9B5S21 compounds are characterized by two types of anions: tetrahedral [BS4]5– and trigonal planar [BS3]3– as well as [(S2–)3] units. Isolated [BS4]5– tetrahedra (all pointing with one of their apices along the polar [001] direction) represent a unique feature of the crystal structure which is observed for the first time in a thioborate compound. These tetrahedra are stacked along the three-fold rotation axes. Vacancies are located at the trigonal-planar coordinated boron site with preferred ordering –B–B––B–B–– along [001]. No superstructure is observed by means of electron diffraction methods as adjacent columns are shuffled along the c axis, giving rise to a randomly distributed vacancy pattern. Positions of the sulfur atoms within the [(S2–)3] substructure as well as planarity of the [BS3]3– units were investigated in more detail by means of quantum mechanical calculations. Results of the IR and Raman spectroscopy, as well as of the 11B NMR spectroscopy are in agreement with the presence of the boron atoms in two different coordination environments. Thermal analyses showed that compounds RE9B5S21 are stable under inert conditions up to ~ 1200 K. In accordance with the combined results of experimental and computational investigations, the chemical formula of the RE9B5S21 compounds is consistent with RE3[BS3]2[BS4]3S3. A short overview of investigations towards rare earth selenoborates, where in most of the cases only known binary rare earth selenides could be identified, is presented as well in this work. Investigations in the RE–B–Se systems were conducted by the application of different preparation routes by varying the experimental parameters and the initial compositions of the starting mixtures. Although no crystal structure of a ternary phase in these systems could be solved, there are indications that such phases exist, but further investigations are needed. [1] M. Döch, A. Hammerschmidt, B. Krebs, Z. Anorg. Allg. Chem., 2004, 630, 519. [2] H. Huppertz, Chem. Commun., 2011, 47, 131; and references therein. [3] J. Hunger, M. Borna, R. Kniep, J. Solid State Chem., 2010, 182, 702; J. Hunger, M. Borna, R. Kniep, Z. Kristallogr. NCS, 2010, 225, 217; M. Borna, J. Hunger, R. Kniep, Z. Kristallogr. NCS, 2010, 225, 223; M. Borna, J. Hunger, R. Kniep, Z. Kristallogr. NCS, 2010, 225, 225. [4] M. Borna, J. Hunger, A. Ormeci, D. Zahn, U. Burkhardt, W. Carrillo-Cabrera, R. Cardoso-Gil, R. Kniep, J. Solid State Chem., 2011, 184, 296; [5] H. Müller-Bunz, T. Nikelski, Th. Schleid, Z. Naturforsch. B, 2003, 58, 375. [6] H. U. Bambauer, J. Weidelt, J.-St. Ysker, Z. Kristallogr., 1969, 130, 207. [7] D. de Saint-Giniez, P. Laruelle, J. Flahaut, C. R. Séances, Acad. Sci. Ser. C, 1968, 267, 1029.

No description available.

Thèse numérisée par la Division de la gestion de documents et des archives de l'Université de Montréal

Εξαιτίας των πολλών εφαρμογών του καδμίου στη βιομηχανία αλλά και των ταυτόχρονα τοξικών ιδιοτήτων του στα έμβια όντα, η απομάκρυνση του Cd(II) από υδατικά απόβλητα είναι σήμερα ένα ενδιαφέρον θέμα έρευνας στην Περιβαλλοντική Χημεία. Η υγρή εκχύλιση (εκχύλιση με διαλύτη) είναι μια αποτελεσματική μέθοδος για την απομάκρυνση του Cd(II) από διαλύματα που περιέχουν ιόντα χλωριδίων, θειικά ή φωσφορικά διαλύματα. Κατά την υγρή εκχύλιση το μεταλλοϊόν συμπλοκοποιείται με έναν οργανικό υποκαταστάτη σχηματίζοντας ένα χημικό είδος που μεταφέρεται από την υδατική στην οργανική φάση σε ένα διφασικό σύστημα. Αναφέρθηκε πρόσφατα ότι το κάδμιο(II) μπορεί να εκχυλιστεί από μέσα που περιέχουν ιόντα χλωριδίων ή ιόντα χλωριδίων/νιτρικών χρησιμοποιώντας δύο 2-πυρίδυλο κετονοξίμες, και συγκεκριμένα την 1-(2-πυριδυλο)-δεκατρια-1-όνη οξίμη (2PC12) και την 1-(2-πυριδυλο)-δεκαπεντε-1-όνη (2PC14), ως μέσα εκχύλισης. Ο στόχος αυτής της εργασίας είναι να μοντελοποιήσει την φύση των χημικών ειδών που σχηματίζονται κατα την διαδικασία της υγρής εκχύλισης του Cd(II) χρησιμοποιώντας 2-πυρίδυλο κετονοξίμες ως μέσα εκχύλισης. Έτσι μελετήσαμε τις αντιδράσεις διαφόρων πηγών Cd(II) με 2-πυρίδυλο οξίμες ως υποκαταστάτες (Σχήμα I). Οι υποκαταστάτες που χρησιμοποιήθηκαν ήταν οι 2-πυριδίνη αλδοξίμη (paoH), μέθυλο 2-πυρίδυλο κετονοξίμη (mepaoH), φαίνυλο 2-πυρίδυλο κετονοξίμη (phpaoH) και πυριδινη-2-αμιδοξίμη (ampaoH). Η συστηματική συνθετική μας διερεύνηση οδήγησε στα προϊόντα [CdI2(paoH)2] (1), [Cd(NO3)2(paoH)2] (2), [Cd(NO3)(H2O)(paoH)2](NO3) (3), [Cd(paoH)3](ClO4)2 (4), [Cd(pao)2(paoH)2] (5), [CdI2(mepaoH)2] (6), [Cd(NO3)2(mepaoH)2] (7), [Cd(O2CMe)2(mepaoH)2] (8), [CdCl2(phpaoH)2] (9), [Cd4Br8(phpaoH)4]n (10), [CdI2(phpaoH)2] (11), [Cd(NO3)2(phpaoH)2] (12), [Cd2(Ο2CMe)4(phpaoH)2]n (13), [CdCl2(ampaoH)2] (14), [CdBr2(ampaoH)2] (15), [CdI2(ampaoH)2] (16) και [Cd(NO3)2(ampaoH)2] (17). Οι μοριακές και κρυσταλλικές δομές των συμπλόκων προσδιορίστηκαν με κρυσταλλογραφία ακτίνων Χ επί μονοκρυστάλλων των ενώσεων (Σχήμα II). Τα σύμπλοκα χαρακτηρίσθηκαν με στοιχειακές αναλύσεις και διάφορες φασματοσκοπικές μεθόδους (IR, Raman, NMR, Φωτοφωταύγεια). Τα φασματοσκοπικά δεδομένα μελετήθηκαν σε σχέση με τις γνωστές δομές των ενώσεων. Tα περισσότερα σύμπλοκα είναι μονοπυρηνικά. Οι ενώσεις 10 και 13 είναι 1D πολυμερή ένταξης. Τα μόρια paoH, mepaoH, phpaoH και ampaoH συμπεριφέρονται ως Ν(πυρίδυλο), Ν(οξιμικό)-διδοντικοί χηλικοί υποκαταστάτες. Τα ιόντα CdII στα σύμπλοκα είναι 6-, 7- και 8-ενταγμένα. Οι κρυσταλλικές δομές των περισσοτέρων συμπλόκων σταθεροποιούνται από δεσμούς Η. Τα περισσότερα σύμπλοκα διασπώνται στο DMSO, όπως προκύπτει από τα 1Η ΝΜR φάσματά τους. Τα σύμπλοκα 9, 14 και 12, 17 μοντελοποιούν τα χημικά είδη [CdCl2(μέσο εκχύλισης)2] και [Cd(NO3)2(μέσο εκχύλισης)2] που έχει προταθεί ότι σχηματίζονται κατά τη διαδικασία της υγρής εκχύλισης του Cd(II) με τη χρησιμοποίηση των 2PC12 και 2PC14 σε διαλύματα χλωριδίων και χλωριδίων/νιτρικών, αντίστοιχα. Με επιφύλαξη προτείνουμε ότι η ικανότητα των 2-πυρίδυλο κετοξιμών να απομακρύνουν Cd(II) από υδατικά απόβλητα οφείλεται στην ισχυρά χηλική φύση των μέσων εκχύλισης. / Because of the wide application of cadmium in various industrial facilities and its simultaneous toxic properties for organisms, the removal of Cd(II) from wastewater is a currently hot topic in environmental chemistry. Solvent extraction is an efficient method from the removal of Cd(II) from chloride, sulfate or phosphate solutions. Solvent extraction occurs when a metal ion is coordinated to an organic ligand to form a species that is transferred from the aqueous to the organic phase in a two-phase system. It has recently been reported that cadmium(II) can be extracted from chloride or chloride/nitrate media using two 2-pyridyl ketoximes, namely 1-(2-pyridyl)-trideca-1-one oxime (2PC12) and 1-(2-pyridyl)-pentadeca-one oxime (2PC14), as extractants and chloroform or hydracarbons as organic solvents [A. Parus, K. Wieszczycka, A. Olszanowski (2011) Hydrometallurgy, 105, 284]. The goal of this work is to model the nature of the chemical species that are formed during the solvent extraction of Cd(II) using 2-pyridyl ketoximes as extractants. Thus, we studied the reactions of various Cd(II) sources with 2-pyridyl oximes as ligands (Scheme I). The ligands used were 2-pyridine aldoxime (paoH), methyl 2-pyridyl ketoxime (mepaoH), phenyl 2-pyridyl ketoxime (phpaoH) and pyridine-2-amidoxime (ampaoH). Our systematic investigations gave the products [CdI2(paoH)2] (1), [Cd(NO3)2(paoH)2] (2), [Cd(NO3)(H2O)(paoH)2](NO3) (3), [Cd(paoH)3](ClO4)2 (4), [Cd(pao)2(paoH)2] (5), [CdI2(mepaoH)2] (6), [Cd(NO3)2(mepaoH)2] (7), [Cd(O2CMe)2(mepaoH)2] (8), [CdCl2(phpaoH)2] (9), [Cd4Br8(phpaoH)4]n (10), [CdI2(phpaoH)2] (11), [Cd(NO3)2(phpaoH)2] (12), [Cd2(Ο2CMe)4(phpaoH)2]n (13), [CdCl2(ampaoH)2] (14), [CdBr2(ampaoH)2] (15), [CdI2(ampaoH)2] (16) and [Cd(NO3)2(ampaoH)2] (17). The molecular and crystal structures of the complexes have been determined by single-crystal, X-ray crystallography (Scheme II). The complexes have been characterized by elemental analyses and various spectroscopic techniques (IR, Raman, NMR, Photoluminescence). The spectroscopic data are discussed in terms of the known structures. Most complexes are mononuclear. Compounds 10 and 13 are 1D coordination polymers. The paoH, mepaoH, phpaoH and ampaoH molecules behave as N(pyridyl), N(oxime)–bidentate chelating ligands. The CdII ions in the complexes are 6-, 7- and 8-coordinate. The crystal structures of most complexes are stabilized by H bonds. Most of the complexes decompose in DMSO, as evidenced by 1H NMR spectroscopy. Complexes 9, 14 and 12, 17 model the chemical species [CdCl2(extractant)2] and [Cd(NO3)2(extractant)2] that have been proposed to form during the solvent extraction of Cd(II) using 2PC12 and 2PC14 in chloride and dilute chloride/concentrated nitrate solutions, respectively. We tentatively propose that the ability of 2-pyridyl ketoximes to remove Cd(II) from wastewater is due to the strongly chelating nature of the extractants.

Chimie organométallique résonne avec catalyse homogène, et chimie des surfaces avec catalyse hétérogène. Mais la frontière établie entre ces deux domaines est en réalité très mince. Leur rapprochement aboutit dans les années 1990 au développement d’une nouvelle science : la chimie organométallique de surface, qui souligne leur complémentarité. L’objectif de cette science, dans laquelle s’inscrit ce travail de thèse, est de créer des catalyseurs hétérogènes à partir de composés organométalliques. Notre objectif est d’apporter une contribution à la compréhension de la formation de nanoparticules de platine - métal incontournable en catalyse hétérogène - sur des supports de silice amorphe, et ce grâce à la chimie organométallique. Au cours de ce travail, une palette de catalyseurs Pt/SiO2 a été préparée à partir de trois précurseurs de platine : le composé classique H2PtIVCl6.xH2O et deux composés organométalliques PtII(η 4-C8H12)Cl2 et Pt0(η 2-C7H10)3 , et de trois supports : une silice commerciale (Davison), une silice mésoporeuse SBA-15 synthétisée au laboratoire et unesilice naturelle, la diatomite. De plus, l’étude du catalyseur de référence au platine « EuroPt-1 » a permis de développer une méthodologie de suivi operando par Spectroscopie Infrarouge à Transformée de Fourier par Réflexion Diffuse (DRIFTS) de l’adsorption du monoxyde de carbone (CO) sur les différents sites d’une nanoparticule de platine. En conclusion, les catalyseurs préparés à partir de Pt0(η 2-C7H10)3 s’avèrent être plus actifs qu’EuroPt-1 pour la réaction d’oxydation du CO, ce qui démontre le potentiel d’utilisation des composés organométalliques dans le domaine de la catalyse hétérogène. / Organometallic chemistry resonates with homogeneous catalysis, and surface chemistry with heterogeneous catalysis. But the frontier between these two fields is very thin. In the 90’s, these fields approached each other and led to the development of a new science: organometallic surface chemistry, which underlines their complementarity. The goal of this science, with which this work is associated, is to create heterogeneous catalysts from organometallic compounds. Our goal is to contribute to the understanding of platinum nanoparticle formation - platinum being an important metal in heterogeneous catalysis - onto amorphous silica supports, thanks to organometallic chemistry. During this work, various Pt/SiO2 catalysts were prepared fromthree platinum precursors: the classical one, H2PtIVCl6.xH2O and two organometallic compounds PtII(η 4-C8H12)Cl2 et Pt0(η2-C7H10)3, and involved three supports: a commercial silica (Davison), a mesoporous silica SBA-15 synthesized in the laboratory, and a natural silica, the diatomite. Moreover, the study of the standard platinum reference catalyst “EuroPt-1” lead to the development of a methodology of operando Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) of carbon monoxide (CO) adsorption on the different sites of a platinum nanoparticle. Catalysts prepared from Pt0(η 2-C7H10)3 are more active than EuroPt-1 for the CO oxidation reaction, and this work shows the potential of organometallic precursors in the domain of heterogeneous catalysis.

For the first time, successful synthesis of an unknown class of compounds, 3-azido-2H-azirines, which are implicated as highly reactive intermediates in the thermolysis of the corresponding 1,1-diazidoethenes, has been performed. These elusive heterocycles have been detected and characterised by low-temperature NMR and in situ IR spectroscopy. Even the parent compound, 3-azido-2H-azirine, has been observed via low-temperature photolysis of 1,1-diazidoethene, as a highly reactive species with a half-life period of only 12 min at −40 °C. / Dieser Beitrag ist aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.