Late Transition Metal-Oxo complexes: Synthesis, and Biorelevant Reactivity

High-valent terminal metal-oxygen adducts are supposed to be potent oxidising intermediates in enzymatic catalyses. In contrast to those from groups 6-8, oxidants that contain late transition metals (Co, Ni, Cu) are poorly understood. Because of their high reactivity, only a few examples of these compounds have been observed. The aim of this project was to investigate the reactivity of high-valent Ni(III) complexes, containing a monodentate oxygen-donor ligands, in hydrogen atom abstraction (HAA) and oxygen atom transfer (OAT) reactions which are typical of biological high-valent metal-oxygen species. Particularly, the Ni(III) complexes were generated in situ, at low temperature, from the oxidation of the Ni(II) species.The nickel complexes studied during this work were supported by tridentate ligands, with a strong σ-donating ability and exceedingly resistant to several common degradation pathways. These complexes vary based on the monodentate group in the fourth coordination position site, which can be neutral or anionic. In particular, we prepared four different Ni(III) complexes [NiIII(pyN2Me2)(OCO2H)] (12), [NiIII(pyN2Me2)(ONO2)] (14), [NiIII(pyN2Me2)(OC(O)CH3)] (18) and [NiIII(pyN2Me2)(OC(O)H)] (25). They feature a bicarbonate (-OCO2H), nitrate (-ONO2), acetate (-OC(O)CH3) and formate (-OC(O)H) group, respectively.HAA and OAT reactions were performed by adding 2,6-di-tert-butylphenol (2,6-DTBP) at -40°C, and triphenylphosphine (PPh3) at -80°C, to the in situ generated Ni(III) complexes, respectively. These reactions were carried out by adding 7 to 500 equivalents of substrate, in order to ensure pseudo-first order conditions. Since, the reactivity of the Ni(III) complex featured by the bicarbonate group has been studied in a previous work, we only investigated that of the species bearing the nitrate, acetate and formate ligand. Finally we compared the value of the reaction rate of all the four species in the HAA and OAT reactions.

Ab-initio determination of x-ray absorption near edge structure (xanes) spectra in an ultrasoft and norm conserving pseudopotentials scheme

X-ray absorption spectroscopy (XAS) is a powerful means of investigation of structural and electronic properties in condensed -matter physics. Analysis of the near edge part of the XAS spectrum, the so – called X-ray Absorption Near Edge Structure (XANES), can typically provide the following information on the photoexcited atom: - Oxidation state and coordination environment. - Speciation of transition metal compounds. - Conduction band DOS projected on the excited atomic species (PDOS). Analysis of XANES spectra is greatly aided by simulations; in the most common scheme the multiple scattering framework is used with the muffin tin approximation for the scattering potential and the spectral simulation is based on a hypothetical, reference structure. This approach has the advantage of requiring relatively little computing power but in many cases the assumed structure is quite different from the actual system measured and the muffin tin approximation is not adequate for low symmetry structures or highly directional bonds. It is therefore very interesting and justified to develop alternative methods. In one approach, the spectral simulation is based on atomic coordinates obtained from a DFT (Density Functional Theory) optimized structure. In another approach, which is the object of this thesis, the XANES spectrum is calculated directly based on an ab – initio DFT calculation of the atomic and electronic structure. This method takes full advantage of the real many-electron final wavefunction that can be computed with DFT algorithms that include a core-hole in the absorbing atom to compute the final cross section. To calculate the many-electron final wavefunction the Projector Augmented Wave method (PAW) is used. In this scheme, the absorption cross section is written in function of several contributions as the many-electrons function of the finale state; it is calculated starting from pseudo-wavefunction and performing a reconstruction of the real-wavefunction by using a transform operator which contains some parameters, called partial waves and projector waves. The aim of my thesis is to apply and test the PAW methodology to the calculation of the XANES cross section. I have focused on iron and silicon structures and on some biological molecules target (myoglobin and cytochrome c). Finally other inorganic and biological systems could be taken into account for future applications of this methodology, which could become an important improvement with respect to the multiscattering approach.

Ex situ X-­Ray absorption study of Li-­rich layered cathode material Li[Li0.2Mn0.56Ni0.16Co0.08]O2

The Li-rich layered transition metal oxides (LLOs) Li2MnO3-LiMO2 (M=Mn, Co, Ni, etc.) have drawn considerable attention as cathode materials for rechargeable lithium batteries. They generate large reversible capacities but the fundamental reaction mechanism and structural perturbations during cycling remain controversial. In the present thesis, ex situ X-ray absorption spectroscopy (XAS) measurements were performed on Li[Li0.2Mn0.56Ni0.16Co0.08]O2 at different stage of charge during electrochemical oxidation/reduction. K-edge spectra of Co, Mn and Ni were recorded through a voltage range of 3.7-4.8V vs. Li/Li+, which consist of X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). Oxidation states during initial charge were discussed based on values from literature as well as XANES analysis. Information about bond distance, coordination number as well as corresponding Debye-Waller factor were extracted from Gnxas analysis of raw data in the EXAFS region. The possibility of oxygen participation in the initial charge was discussed. Co and Ni prove to take part in the oxidation/reduction process while Mn remain in the tetravalent state. The cathode material appears to retain good structural short-range order during charge-discharge. A resemblance of the pristine sample and sample 4 was discovered which was firstly reported for similar compounds.

Small polarons in spin-orbit coupled osmates

Small polarons (SP) have been thoroughly investigated in 3d transition metal oxides and they have been found to play a crucial role in physical phenomena such as charge transport, colossal magnetoresistance and surface reactivity. However, our knowledge about these quasi-particles in 5d systems remains very limited, since the more delocalised nature of the 5d orbitals reduces the strength of the Electronic Correlation (EC), making SP formation in these compounds rather unexpected. Nevertheless, the Spin-Orbit coupled Dirac-Mott insulator Ba2NaOsO6 (BNOO) represents a good candidate for enabling polaron formation in a relativistic background, due to the relatively large EC (U ∼ 3 eV) and Jahn-Teller activity. Moreover, anomalous peaks in Nuclear Magnetic Resonance (NMR) spectroscopy experiments suggest the presence of thermally activated SP dynamics when BNOO is doped with Ca atoms. We investigate SP formation in BNOO both from an electronic and structural point of view by means of fully relativistic first principles calculations. Our numerical simulations predict a stable SP ground state and agree on the value of 810 K for the dynamical process peak found by NMR experiments.

Design e sintesi di nuove sonde luminescenti per il "targeting" dell'avidina

Recent studies on the use of bio-conjugating organometallic probes report on the possibility to use biotinylated-derivatives to selectively coordinate to a specific protein, avidin. In the present thesis, the synthesis of four new bifunctional ligands is described. The ligands contain both a pyridine triazolic unit able to coordinate a transition metal, and a biotin fragment able to bond avidin: the two functionalities are linked together by an appropriate aromatic linker (amide or ester). The obtained ligands were then employed to form luminescent Ir(III) complexes, that have been fully characterized also by a photophysical point of view both in organic and in aqueous solvent. Therefore, titrations of solutions of avidin with aqueous solutions of Ir(III)-complexes have been performed in order to estimate the luminescence variations of the complexes in the presence or in the absence of bio-conjugation.

Complessi carbenici N-eterociclici di rutenio: catalizzatori omogenei in reazioni di idrogenazione e deidrogenazione

Il presente lavoro di tesi si inserisce in un progetto di ricerca volto alla sintesi di nuovi complessi di metalli di transizione per lo sviluppo di catalizzatori bifunzionali metallo-legante da impiegare in reazioni di catalisi omogenea, in particolare in reazioni redox quali idrogenazione e deidrogenazione attraverso il trasferimento di idrogeno. Il mio progetto ha riguardato la messa a punto della sintesi di complessi di Ru(0) che combinano leganti ciclopentadienonici e carbeni N-eterociclici e la sintesi dei corrispondenti complessi cationici per protonazione. Inoltre, è stato sintetizzato e caratterizzato un nuovo complesso cationico attraverso la metilazione del corrispettivo complesso neutro. I complessi sintetizzati sono stati utilizzati come precursori di catalizzatori nella riduzione tramite trasferimento di idrogeno del 4-fluoroacetofenone, valutandone l’attività catalitica in relazione a leganti, additivi e controioni. Allo scopo di delineare qualche ipotesi sul meccanismo di reazione sono stati effettuati diversi studi sulla reattività dei complessi impiegati in catalisi, in particolare usando la piridina come agente di “trapping”. Infine, è stato condotto uno studio preliminare dell’attività catalitica dei complessi sintetizzati nell’ossidazione di benzilalcol a benzaldeide. The present work is part of a research project that involves the study of new ruthenium-based transition metal complexes in order to develop new metal-ligand bifunctional catalysts to employ in homogeneous catalytic systems, in particular in redox reactions such as hydrogenation and dehydrogenation through hydrogen transfer. My project is focused on the optimization of the synthesis of Ru(0) complexes that combines different ligands as tetraphenylcyclopentadienone and N-heterocyclic carbenes and the synthesis of the corresponding cationic complexes by protonation. Furthermore, it is reported the synthesis and characterization of a new cationic complex obtained by methylation of the corresponding neutral complex. All the prepared complexes were employed as catalyst precursors in the transfer hydrogenation of 4-fluoroacetophenone and their performances were investigated in relation to the type of ligands, additives and counterions. The reactivity of these ruthenium complexes was also investigated with the aim of delineate some hypothesis on the reaction mechanism, in particular employing pyridine as a trapping agent. Finally, preliminary studies on the oxidation of benzyl alcohol have been carried out.

Synthesis of manganese organometallic complexes

Il presente lavoro di tesi si inserisce in un progetto di ricerca volto alla sintesi di nuovi complessi di metalli di transizione per lo sviluppo di catalizzatori da impiegare in reazioni di catalisi omogenea. In particolare il mio progetto si è concentrato sulla sintesi di complessi organometallici di manganese con leganti carbenici N-eterociclici (NHC). La scelta dei leganti è stata effettuata in modo tale da poter avere leganti chelanti NHC di tipo MIC (mesoionic carbene) sintetizzati tramite cicloaddizione tra un alchino ed un azide catalizzata da rame (CuAAC) e N-alchilazione. Lo studio di questi complessi a base di manganese è ancora tutt’oggi agli albori, leganti NHC vengono molto utilizzati grazie alla possibilità di variarne le proprietà steriche ed elettroniche e alla possibilità di formare legami forti con quasi tutti i metalli. Il manganese è stato scelto poiché un elemento abbondante, poco tossico e poco costoso. The present thesis work is part of a research project aimed at the synthesis of new transition metal complexes to be used in homogeneous catalysis reactions. In particular my project focused on the synthesis of manganese organometallic complexes with N-heterocyclic carbene ligands (NHC). The choice of ligands was carried out to have NHC chelating ligands of the class of MIC (mesoionic carbene). These ligands are synthesized by cycloaddition between alkyl and azide with a copper-catalyzed reaction (CuAAC) and N-alkylation in order to obtain MIC after deprotonation. The study of these manganese-based complexes is still in its infancy today, NHC ligands are widely used thanks to the possibility of varying their steric and electronic properties and the possibility of forming strong bonds with almost all metals. The choice of manganese was made because is an abundant, low-toxic and inexpensive element.

Synthesis and metal complexes of C2 symmetric ligands obtained from (R)-(+)-Betti and dialdehydes for asymmetric induction reactions

The aim of this master’s research thesis was the employment of an enantiopure 1,3-aminoalcohol, the 1-(α-aminobenzyl)-2-naphthol, known as Betti base, for the synthesis of some novel compounds which show a C2 symmetry. Some of these compounds, after derivatization, were used as ligands in association with transition metals to prepare some catalysts for enantioselective catalytic reactions. Some aminoalcohol (Salan-type) derivatives of these compounds were obtained upon reduction and in some cases it was possible to obtain complexes with transition metals such as Mn, Ni, Co and Cu. Furthermore a novel 6-membered analogue bisoxazoline ligand, 2,6-bis((R)-1-Phenyl-1H-naphtho[1,2-e][1,3]oxazin-3-yl)pyridine, was obtained and from it two Cu-complexes were prepared. The metal complexes were employed in some reactions to test the asymmetric induction, which was in some cases up to discrete values.

Synthesis and surface characterization of metal (Mn, Ti) hexacyanoferrate electrodes

Due to the limited resources of lithium, new chemistries based on the abundant and cheap sodium and even zinc have been proposed for the battery market. Prussian Blue Analogues (PBAs) are a class of compounds which have been explored for many different applications because of their intriguing electrochemical and magnetic properties. Manganese and titanium hexacyanoferrate (MnHCF and TiHCF) belong to the class of PBAs. In this work, MnHCF and TiHCF electrodes were synthetized, cycled with cyclic voltammetry (CV) in different setups and subsequently, the surfaces were characterized with X-ray Photoelectron Spectroscopy (XPS). The setups chosen for CVs were coin cell with zinc aqueous solution for the MnHCF series, three-electrode cell and symmetric coin cell with sodium aqueous solution for the TiHCF series. The electrodes were treated with different number of cycles to evaluate the chemical changes and alterations in oxidation states during cycling.

Study of the absorption of organic compounds on biopolymers

This work has been conducted in order to determine the solubility and diffusion coefficients of different aromatic substances in two different grades of polylactic acid (PLA), Amorphous (PDLLA) and Crystalline (PLLA); in particular the focus is on the following terpenes: Linalool, α-Pinene, β-Citronellol and L-Linalool. Moreover, further analyses have been carried out with the aim to verify if the use of neat crystalline PLA, (PLLA), a chiral substrate, may lead to an enantioenrichment of absorbed species in order to use it as membrane in enantioselective processes. The other possible applications of PLA, which has aroused interest in carry out the above-mentioned work, concerns its use in food packaging. Therefore, it is interesting and also very important, to evaluate the barrier properties of PLA, focusing in particular on the transport and absorption of terpenes, by the packaging and, hence, by the PLA. PLA films/slabs of one-millimeter thickness and with square shape, were prepared through the Injection Molding process. On the resulting PLA films heat pretreatment processes of normalizing were then performed to enhance the properties of the material. In order to evaluate solubility and diffusion coefficient of the different penetrating species, the absorption kinetics of various terpenes, in the two different types of PLA, were determined by gravimetric methods. Subsequently, the absorbed liquid was extracted with methanol (MeOH), non- solvent for PLA, and the extract analyzed by the use of High Performance Liquid Chromatography (HPLC), in order to evaluate its possible enantiomeric excess. Moreover, PLA films used were subjected to differential scanning calorimetry (DSC) which allowed to measure the glass transition temperature (Tg) and to determine the degree of crystallinity of the polymer (Xc).