Solvent Influences on the Molecular Aggregation of Magnesium Aryloxides (open access)

Solvent Influences on the Molecular Aggregation of Magnesium Aryloxides

Magnesium aryloxides were prepared in a variety of solvents through the reaction of dibutyl magnesium with sterically varied aryl alcohols: 2,6-dimethylphenol (H-DMP), 2,6-diisopropylphenol (H-DIP), and 2,4,6-trichlorophenol (H-TCP). Upon using a sufficiently strong Lewis-basic solvent, the monomeric species Mg(DMP){sub 2}(py){sub 3} (1, py = pyridine), Mg(DIP){sub 2}(THF){sub 3}, (2a, THF = tetrahydrofuran) Mg(TCP){sub 2}(THF){sub 3} (3) were isolated. Each of these complexes possesses a five-coordinate magnesium that adopts a trigonal bipyramidal geometry. In the absence of a Lewis base, the reaction with H-DIP yields a soluble trinuclear complex, [Mg(DIP){sub 2}]{sub 3} (2b). The Mg metal centers in 2b adopt a linear arrangement with a four-coordinate central metal while the outer metal centers are reduced to just three-coordinate. Solution spectroscopic methods suggest that while 2b remains intact, the monomeric species (1, 2a, and 3) are involved in equilibria, which facilitate intermolecular ligand transfer.
Date: July 14, 2000
Creator: Zechmann, Cecilia A.; Boyle, Timothy J.; Rodriguez, Mark A. & Kemp, Richard A.
Object Type: Article
System: The UNT Digital Library
Near Field Environment Process Model Report (open access)

Near Field Environment Process Model Report

Waste emplacement and activities associated with construction of a repository system potentially will change environmental conditions within the repository system. These environmental changes principally result from heat generated by the decay of the radioactive waste, which elevates temperatures within the repository system. Elevated temperatures affect distribution of water, increase kinetic rates of geochemical processes, and cause stresses to change in magnitude and orientation from the stresses resulting from the overlying rock and from underground construction activities. The recognition of this evolving environment has been reflected in activities, studies and discussions generally associated with what has been termed the Near-Field Environment (NFE). The NFE interacts directly with waste packages and engineered barriers as well as potentially changing the fluid composition and flow conditions within the mountain. As such, the NFE defines the environment for assessing the performance of a potential Monitored Geologic Repository at Yucca Mountain, Nevada. The NFe evolves over time, and therefore is not amenable to direct characterization or measurement in the ambient system. Analysis or assessment of the NFE must rely upon projections based on tests and models that encompass the long-term processes of the evolution of this environment. This NFE Process Model Report (PMR) describes the analyses …
Date: November 14, 2000
Creator: Wagner, R. A.
Object Type: Report
System: The UNT Digital Library