| This dissertation is comprised of 13 chapters, and where appropriate, additional tables and figures have been placed in the corresponding appendix (at the back of the chapter). Each chapter opens with its abstract. The material in this dissertation is primarily related to the structural and physical study of metalloporphyrins and polyoxometalates (Keggin ions), with Chapters 12 and 13 being exceptions. Chapter 12 presents a structural study of an affinity chromatographic linker reagent, 4-(oxyacetyl)phenoxyacetic acid. Chapter 13 contains crystallographic studies of two related molecules, a hypervalent iodonium ylide, phenyldimedonyliodone water and its thermal rearrangement product, the phenyl ether of iododimedone.; Collaborative efforts have provided additional information pertaining to redox photochemistry of polyoxometalates and as well as the thermal oxidation of hydrocarbons by metalloporphyrins. In each chapter crystallographic X-ray diffraction data firmly establish the solid state identity of the chemical specie under study. Most of the metalloporphyrins have 5, 10, 15, 20-tetraphenylporphyrin (TPP('-2)) as the dianion (Chapter 11 is the only exception where the dianion is 5, 10, 15, 20-tetrakis 2,6-(dichlorophenyl)porphyrin (TDCPP('-2)) ). the manganese(III) porphyrin complexes provide structural/physical information concerning the coordination of manganese(III) to O-bound neutral ligands (N,N-dimethylformamide (Chapter 1), 2,6-lutidine N-oxide (Chapter 2), N-methylmorpholine N-oxide (Chapter 8), water (Chapters 7 and 9) and dimethyl sulfoxide (Chapter 10)). Many of these complexes represent new structurally characterized coordination forms of manganese porphyrins. These structural models are not only of significance to cytochrome P-450 (i.e. catalytic organic oxygenation processes), but also of relevance to water oxidation and oxygen evolution by manganese porphyrins (Chapters 7 and 9). Frequently, new insights have been gained pertaining to manganese(III) and zinc(II) porphyrin stereochemistry. Where pertinent, physical characterization included techniques such as ('1)H NMR, ultraviolet-visible, and infrared spectroscopy.; Chapter 6 concludes the polyoxometalate studies with a detailed comparison of the various electron-donor-acceptor complexes (N,N-dimethylacetamide (Chapter 4), 1,1,3,3-tetramethylurea (Chapter 5 and 6). The end of Chapter 10 summarizes some of the structural information (d(,Mn-O(axial)) bond lengths and d(,Mn-N(pyrrole)) bond lengths) determined from the manganese(III) structures presented in this dissertation. |
