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.

Optimization of Processing Technology for Commercial Drying of Bananas (Matooke)

Summary - Cooking banana is one of the most important crops in Uganda; it is a staple food and source of household income in rural areas. The most common cooking banana is locally called matooke, a Musa sp triploid acuminate genome group (AAA-EAHB). It is perishable and traded in fresh form leading to very high postharvest losses (22-45%). This is attributed to: non-uniform level of harvest maturity, poor handling, bulk transportation and lack of value addition/processing technologies, which are currently the main challenges for trade and export, and diversified utilization of matooke. Drying is one of the oldest technologies employed in processing of agricultural produce. A lot of research has been carried out on drying of fruits and vegetables, but little information is available on matooke. Drying of matooke and milling it to flour extends its shelf-life is an important means to overcome the above challenges. Raw matooke flour is a generic flour developed to improve shelf stability of the fruit and to find alternative uses. It is rich in starch (80 - 85%db) and subsequently has a high potential as a calorie resource base. It possesses good properties for both food and non-food industrial use. Some effort has been done to commercialize the processing of matooke but there is still limited information on its processing into flour. It was imperative to carry out an in-depth study to bridge the following gaps: lack of accurate information on the maturity window within which matooke for processing into flour can be harvested leading to non-uniform quality of matooke flour; there is no information on moisture sorption isotherm for matooke from which the minimum equilibrium moisture content in relation to temperature and relative humidity is obtainable, below which the dry matooke would be microbiologically shelf-stable; and lack of information on drying behavior of matooke and standardized processing parameters for matooke in relation to physicochemical properties of the flour. The main objective of the study was to establish the optimum harvest maturity window and optimize the processing parameters for obtaining standardized microbiologically shelf-stable matooke flour with good starch quality attributes. This research was designed to: i) establish the optimum maturity harvest window within which matooke can be harvested to produce a consistent quality of matooke flour, ii) establish the sorption isotherms for matooke, iii) establish the effect of process parameters on drying characteristics of matooke, iv) optimize the drying process parameters for matooke, v) validate the models of maturity and optimum process parameters and vi) standardize process parameters for commercial processing of matooke. Samples were obtained from a banana plantation at Presidential Initiative on Banana Industrial Development (PIBID), Technology Business Incubation Center (TBI) at Nyaruzunga – Bushenyi in Western Uganda. A completely randomized design (CRD) was employed in selecting the banana stools from which samples for the experiments were picked. The cultivar Mbwazirume which is soft cooking and commonly grown in Bushenyi was selected for the study. The static gravitation method recommended by COST 90 Project (Wolf et al., 1985), was used for determination of moisture sorption isotherms. A research dryer developed for this research. All experiments were carried out in laboratories at TBI. The physiological maturity of matooke cv. mbwazirume at Bushenyi is 21 weeks. The optimum harvest maturity window for commercial processing of matooke flour (Raw Tooke Flour - RTF) at Bushenyi is between 15-21 weeks. The finger weight model is recommended for farmers to estimate harvest maturity for matooke and the combined model of finger weight and pulp peel ratio is recommended for commercial processors. Matooke isotherms exhibited type II curve behavior which is characteristic of foodstuffs. The GAB model best described all the adsorption and desorption moisture isotherms. For commercial processing of matooke, in order to obtain a microbiologically shelf-stable dry product. It is recommended to dry it to moisture content below or equal to 10% (wb). The hysteresis phenomenon was exhibited by the moisture sorption isotherms for matooke. The isoteric heat of sorption for both adsorptions and desorption isotherms increased with decreased moisture content. The total isosteric heat of sorption for matooke: adsorption isotherm ranged from 4,586 – 2,386 kJ/kg and desorption isotherm from 18,194– 2,391 kJ/kg for equilibrium moisture content from 0.3 – 0.01 (db) respectively. The minimum energy required for drying matooke from 80 – 10% (wb) is 8,124 kJ/kg of water removed. Implying that the minimum energy required for drying of 1 kg of fresh matooke from 80 - 10% (wb) is 5,793 kJ. The drying of matooke takes place in three steps: the warm-up and the two falling rate periods. The drying rate constant for all processing parameters ranged from 5,793 kJ and effective diffusivity ranged from 1.5E-10 - 8.27E-10 m2/s. The activation energy (Ea) for matooke was 16.3kJ/mol (1,605 kJ/kg). Comparing the activation energy (Ea) with the net isosteric heat of sorption for desorption isotherm (qst) (1,297.62) at 0.1 (kg water/kg dry matter), indicated that Ea was higher than qst suggesting that moisture molecules travel in liquid form in matooke slices. The total color difference (ΔE*) between the fresh and dry samples, was lowest for effect of thickness of 7 mm, followed by air velocity of 6 m/s, and then drying air temperature at 70˚C. The drying system controlled by set surface product temperature, reduced the drying time by 50% compared to that of a drying system controlled by set air drying temperature. The processing parameters did not have a significant effect on physicochemical and quality attributes, suggesting that any drying air temperature can be used in the initial stages of drying as long as the product temperature does not exceed gelatinization temperature of matooke (72˚C). The optimum processing parameters for single-layer drying of matooke are: thickness = 3 mm, air temperatures 70˚C, dew point temperature 18˚C and air velocity 6 m/s overflow mode. From practical point of view it is recommended that for commercial processing of matooke, to employ multi-layer drying of loading capacity equal or less than 7 kg/m², thickness 3 mm, air temperatures 70˚C, dew point temperature 18˚C and air velocity 6 m/s overflow mode.