Fundamental Studies of Carbon Oxygen Bond Activation in Nickel Diphosphine Ether Complexes. And, Metallomacrocycles as Ligands: Synthesis and Characterization of Aluminum-Bridged Bisglyoximato Complexes of Iron and Cobalt

In order to develop better catalysts for the cleavage of aryl-X bonds fundamental studies of the mechanism and individual steps of the mechanism have been investigated in detail. As the described studies are difficult at best in catalytic systems, model systems are frequently used. To study aryl-oxygen bond activation, a terphenyl diphosphine scaffold containing an ether moiety in the central arene was designed. The first three chapters of this dissertation focus on the studies of the nickel complexes supported by this diphosphine backbone and the research efforts in regards to aryl-oxygen bond activation.

Chapter 2 outlines the synthesis of a variety of diphosphine terphenyl ether ligand scaffolds. The metallation of these scaffolds with nickel is described. The reactivity of these nickel(0) systems is also outlined. The systems were found to typically undergo a reductive cleavage of the aryl oxygen bond. The mechanism was found to be a subsequent oxidative addition, β-H elimination, reductive elimination and (or) decarbonylation.

Chapter 3 presents kinetic studies of the aryl oxygen bond in the systems outlined in Chapter 2. Using a series of nickel(0) diphosphine terphenyl ether complexes the kinetics of aryl oxygen bond activation was studied. The activation parameters of oxidative addition for the model systems were determined. Little variation was observed in the rate and activation parameters of oxidative addition with varying electronics in the model system. The cause of the lack of variation is due to the ground state and oxidative addition transition state being affected similarly. Attempts were made to extend this study to catalytic systems.

Chapter 4 investigates aryl oxygen bond activation in the presence of additives. It was found that the addition of certain metal alkyls to the nickel(0) model system lead to an increase in the rate of aryl oxygen bond activation. The addition of excess Grignard reagent led to an order of magnitude increase in the rate of aryl oxygen bond activation. Similarly the addition of AlMe3 led to a three order of magnitude rate increase. Addition of AlMe₃ at -80 °C led to the formation of an intermediate which was identified by NOESY correlations as a system in which the AlMe3 is coordinated to the ether moiety of the backbone. The rates and activation parameters of aryl oxygen bond activation in the presence of AlMe3 were investigated.

The last two chapters involve the study of metalla-macrocycles as ligands. Chapter 5 details the synthesis of a variety of glyoxime backbones and diphenol precursors and their metallation with aluminum. The coordination chemistry of iron on the aluminum scaffolds was investigated. Varying the electronics of the aluminum macrocycle was found to affect the observed electrochemistry of the iron center.

Chapter 6 extends the studies of chapter 5 to cobalt complexes. The synthesis of cobalt dialuminum glyoxime metal complexes is described. The electrochemistry of the cobalt complexes was investigated. The electrochemistry was compared to the observed electrochemistry of a zinc analog to identify the redox activity of the ligand. In the presence of acid the cobalt complexes were found to electrochemically reduce protons to dihydrogen. The electronics of the ancillary aluminum ligands were found to affect the potential of proton reduction in the cobalt complexes. These potentials were compared to other diglyoximate complexes.

Treading in Mortimer's footsteps: the geochemical cycling of iron and manganese in Esthwaite water

A study of the geochemical cycling of iron and manganese in a seasonally stratified lake, Esthwaite water is described. This work is based on speculative ideas on environmental redox chemistry of iron which were proposed by C.H. Mortimer in the 1940's. These observations have been verified and some speculations confirmed, along with a new understanding of the manganese cycle, and detailed information on the particulate forms of both iron and manganese. Details on the mechanisms and transformations of iron have also emerged.

Building social and ecological resilience to climate change in Roviana, Solomon Islands: PASAP country activity for Solomon Islands: Brief review: climate change trends and projections for Solomon Islands

As part of the Australian Government’s International Climate Change Adaptation Initiative (ICCAI), the Pacific Adaptation Strategy Assistance Program (PASAP) aims to enhance the capacity of partner countries to assess key vulnerabilities and risks, formulate adaptation strategies and plans, mainstream adaptation into decision-making, and inform robust longterm national planning and decision-making in partner countries. The Department of Climate Change and Energy Efficiency contracted University of Queensland (UQ) and University of California, Santa Barbara (UCSB) to lead the project: “Building social and ecological resilience to climate change in Roviana, Solomon Islands” (2010-2012). Under this project The WorldFish Center was subcontracted to undertake outputs 5 and 6 of Objective three: (5) Review of climate change evidence and projections for the study area and (6) Vulnerability and adaptation assessment for the study area. This report addresses the first of these and comprises a desktop review of climate change evidence and projections for the study area.

Copper, zinc, iron and manganese in sediments and in the rock oyster Saccostrea cucullata in Mumbai coast

Sediment and oyster (Saccostrea cucullata) samples were collected at Dhanda, a fishing village in Mumbai, Maharashtra. The samples were analysed for copper, zinc, iron and manganese contents. Metal concentrations in the sediments and bioaccumulated levels in oysters were correlated. There is no positive correlation between the total sedimentary levels of metals analysed and the bioaccumulated levels of respective metals in oyster. A positive correlation between the bioavailable fractions of zinc, iron and manganese, and the bioaccumulated levels exists. Copper, however, shows a negative correlation with respect to the bioaccumulated levels.

Building damage and repair due to leakage in a deep excavation

The north-south line in Amsterdam is being built underneath the historic centre of the city. Three deep stations are being constructed in deep excavations supported by diaphragm walls. During the excavation for Vijzelgracht station, leakage through the wall resulted in large settlements and damage to historic buildings, which threatened continuation of the project. The authors analysed the cause of the leakage and the damage to the buildings. With the application of robust preventative measures at two of the deep excavations it was possible to continue the project. This paper reports on the cause of the events, the damage to the buildings and the counter-measures taken. It includes lessons learned for the project and for the foundations industry.

Changes in the concentrations of size-fractioned iron and related environmental factors in the northeastern part of lake Dianchi (China)

To observe changes in the concentrations of size-fractionated iron and related environmental factors, experiments were conducted in the northeastern part of the shallow eutrophic lake Dianchi (China) from March 2003 to February 2004. Iron concentrations were measured for three size fractions: particulate iron (phi >0.22 mu m), colloidal iron (phi = 0.025-0.22 mu m) and soluble iron (phi < 0.025 mu m), and environmental factors (physicochemical and biological factors) were synchronously analyzed. Results showed that size-fractionated iron and the related environmental factors all varied with season. Colloidal iron accounted for only 5-9% of total iron, while particulate and soluble iron each accounted for 40-50% of total iron. The results suggested that size-fractionated iron can transform into each other, especially the highly reactive colloidal iron. Significant linear correlations were found between iron in different size fractions, and significant correlations were also obtained between chlorophyll a and environmental factors, such as TN, TP and secchi depth. No significant correlation between iron and chlorophyll a was found in this study.