A range of different heterogeneous catalysts for the isomerisation of ortho-xylene have been prepared and evaluated. These included commercially-available samples, supported metal catalysts and zirconia-based catalysts. The greatest activity was seen for the former, which was found also to be active for a number of related reactions. Zirconia-based catalysts, in particular sulphated zirconia, gave significant activity. It was possible to prepare a catalyst to give 9.5% conversion of ortho-xylene per gram of catalyst with good selectivity to the meta isomer. The catalyst was prepared in two ways, either by the action of ammonium sulphate on "zirconium hydroxide", a hydrated zirconia precursor, or by precipitation from a sulphuric acid-containing solution of zirconium (IV) propoxide. The factors in the synthesis procedure which affect the catalytic performance of the catalyst were investigated. These included choice of reagents, preparative method and calcination procedure. This information was used to prepare an 'idealised' catalyst, which showed activity for a number of reactions of commercial interest. A range of different aminophosphine complexes based on the reaction of a N,N'- substituted diamine with chlorodiphenylphosphine have been prepared for subsequent study as ligands in complexes active in homogeneous catalysis. Palladium and platinum complexes of the type [(diaminodiphosphine)MCl(_2)] have also been prepared and characterised. A number of x-ray diffraction analyses have been performed, which along with other data has allowed the solid state and solution structures to be discussed. The relative reactivities of the ligands have been determined by reactions with manganese pentacarbonyl bromide and also with palladium dichloride complexes. This depends largely on the steric requirements of the ligand in question. The potential of these ligands in catalysis has been evaluated by the performance of their platinum dichloride complexes in the tin (II)-promoted hydroformylation of styrene, and their palladium acetate complexes for the methoxycarbonylation of ethene.

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NMR spectroscopy with in situ laser irradiation has been used to investigate the photo- and thermal isomerisation of eight azobenzene derivatives; diphenyldiazene (azobenzene), p-phenylazoaniline (p-aminoazobenzene), 4-(dimethylamino)azobenzene (Methyl Yellow), 4-dimethylamino-2-methylazobenzene (o-Methyl-Methyl Yellow), p-nitroazobenzene, 4-nitro-4’-dimethylaminoazobeneze (Dimethyl-nitroazobenzene), 4-(4-nitrophenylazo)aniline (Disperse Orange 3) and N-ethyl-N-(2-hydroxyethyl)-4-(4-nitrophenylazo) (Disperse Red 1). The rate constants and activation parameters of the thermal cis-to-trans isomerisation have been measured experimentally and correlated to the mechanism of isomerisation in two solvents. The experimental data show that the values of the activation energy (related to the enthalpy of activation) and the entropy of activation (related to the Arrhenius pre-exponential factor) vary significantly from molecule to molecule and thus both of these parameters influence the inter-molecule variation of the rate constant. Similarly, both of these parameters influence the solvent-dependence of the rate constant. Complementary computational studies have been carried out in the gas phase and in solution using density functional theory (DFT) to predict the structures of the cis and trans isomers and the transition state, and to explore the reaction coordinate. The theoretically predicted activation parameters are compared with those determined experimentally, and the utility of DFT calculations in predicting the effects of molecular structure and solvation on the kinetics of cis-to-trans isomerisation assessed. The DFT-predicted values of the activation energy and Gibbs free energy of activation in DMSO are in good agreement with the experimental values, while the values in benzene tend to be in less good agreement. The DFT calculations are unsuccessful at predicting the entropy of activation, where in all cases there is a large discrepancy between the theoretical and experimental values. The DFT- calculated energy differences between the activation energies of the two inversion pathways for the asymmetric azobenzenes suggests the favourable phenyl ring for inversion. The formation of a linear transition state from a dihedral rotation potential energy curve is explained in terms of the lower activation barrier of the more favourable inversion route (α-inversion) than that of the dihedral rotation pathway, and suggests the inversion through the α-phenyl ring to be the favoured pathway for substituted azobenzene. DFT calculations are able to obtain a transition state corresponding to pure rotation pathway for two azobenzene derivatives. The higher activation barrier for the formation of the transition state corresponding to this pathway compared to that of the formation of the α-transition state confirmed the previous conclusion. DFT predictions of the effect of protonation on the thermal rates of isomerisation of azobenzenes substituted with electron-donating group were in good agreement with the experimental results; both conclude faster isomerisation and lower activation barriers on protonation. However, DFT calculations could not confirm the postulation of rotational transition state for the isomerisation of the protonated molecule, as a result of weakening of the N=N bond by protonation.

Upon treatment with a palladium catalyst and hydrogen gas in the presence of caesium carbonate, a wide range of exomethylenic allylic alcohols were found to afford their corresponding trisubstituted isomers. Although hydrogenation was an unavoidable competing pathway, careful monitoring of the reaction progress allowed the desired isomerised products to be obtained in moderate to excellent yields and high (E):(Z) ratios.

La nécessité de construire des édifices moléculaires complexes s'accompagne d'un besoin de mise au point d'outils synthétiques nouveaux et toujours plus performants. Dans ce contexte, le développement de systèmes photocommutables constitue un moyen privilégié pour la modulation de la réactivité chimique avec un excellent contrôle spatial et temporel. Les complexes organométalliques incorporant des ligands photochromes constituent des candidats de choix pour de telles applications, combinant la réactivité riche du centre métallique avec les propriétés de photocommutation du ligand. Ces travaux de thèse portent sur l'utilisation d'azobenzènes en tant que ligands pour la formation de complexes photocommutables de type (η6-arène)ruthénium. L'étude du comportement d'azobenzènes diversement substitués a conduit à la synthèse d'une nouvelle famille de complexes porteurs d'un ligand o-sulfonamide azobenzène dont les propriétés de photo-isomérisation ainsi que la réactivité ont été étudiées. La coordination de dérivés phosphorés à ces composés peut être modulée sous irradiation lumineuse, et cette propriété a été exploitée pour le photo-déclenchement de la réaction d'aza-Morita-Baylis-Hillman.Dans une seconde partie de ces travaux, nous avons synthétisé une famille d'azobenzènes cycliques pontés par un acétal présentant un processus nouveaux de photo-isomérisation à trois espèces, qui permet l'interconversion sous irradiation lumineuse entre des diastéréoisomères conformationnels stables avec une bonne sélectivité. Ces nouveaux composés offrent des perspectives prometteuses pour le contrôle conformationnel par la lumière. / The growing need to create sophisticated molecules and building blocks requires the development of increasingly more efficient synthetic tools. In this context, photoswitchable systems appear as an ideal means for controlling chemical reactivity with excellent spatial and temporal resolution. Organometallic complexes incorporating photochromic ligands represent a promising class of compounds for such applications as they combine both the versatile reactivity of the metal center with the photoswitchable properties of the ligand. This work investigates the use of azobenzenes as ligands for the synthesis of photoswitchable (η6-arene)ruthenium complexes. The study of the behavior of azobenzenes diversely substituted led to the synthesis of a new family of complexes bearing an o-sulfonamide ligand which photo-isomerization properties were investigated. The coordination of these complexes to phosphorus derivatives could be modulated upon irradiation and this property was applied to the light-triggered aza-Morita-Baylis-Hillman reaction.The second part of this work describes the synthesis and study of a new family of ketal-substituted bridged azobenzenes which display an uncommon three-species photo-isomerization pattern, triggering an interconversion between stable conformational diastereomers with a good selectivity. These compounds offer promising perspectives for conformational control by light.

Student Number : 0009404H - PhD thesis - School of Chemistry - Faculty of Science / Six-coordinate ruthenium complexes of the type ttt-RuX2(RNC)2(PPh3)2 (X = Cl ; R = tBu, 2,6-xylyl, benzyl, 2-OMe-4-Clphenyl and iPr; X = Br; R = = tBu, 2,6-xylyl, benzyl, iPr ) were synthesized and fully characterised by IR, NMR spectroscopy and elemental analysis. These complexes were all found to undergo solid-state isomerisation from the ttt-isomer to the cct-isomer. It was found that solid state isomerisation occurred before melting i.e. in the solid state for all the ttt-RuX2(RNC)2(PPh3)2 complexes investigated . The thermal solid state isomerisation process was monitored by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), thermomicroscopy and X-ray powder diffraction techniques. The results revealed that the isomerisation process occurred exothermally with darkening of the crystal. A mechanism which involved rotation of small ligands was proposed to explain the solid-state isomerisation process. Kinetic studies of the solid-state isomerisation of some of the ttt-RuCl2(RNC)2(PPh3)2 complexes were carried out and monitored by NMR spectroscopy and compared with kinetic studies performed by XRD methods. The results are similar and also suggest that the isomerisation reaction follows first order kinetics. The crystal and molecular structure of ttt-RuCl2(2,6-xylylNC)2(PPh3)2 was determined by X-ray single crystal diffraction techniques and its structure was compared with related ttt- RuX2(RNC)2(PPh3)2 complexes. Inter-molecular and intra-molecular interactions in these molecules in the solid state were analysed and used to rationalise the solid-state isomerisation results. The results obtained for the ruthenium complexes suggested that other six-coordinate complexes could undergo solid state isomerisation reactions and this study was extended to molybdenum complexes of the type cis-Mo(CO)4L2. These complexes undergo cis to trans isomerisation in solution. The solid state reactivity of these complexes was investigated for the first time. The complexes with L = PPh2Me and PPh2Et isomerised in the melt whist complexes with L = PPh3 amd P(m-tolyl)3 were indeed found to undergo solid state isomerisation reactions. Structural studies and thermomicroscopic investigations were done on cis- Mo(CO)4(PPh3)2 and Mo(CO)4{P(m-tolyl)3)2 and the results were used to rationalize the solid state reactivity of these complexes.