Syntheses and reactivity studies on the MoCl(2)(O)(x)O(2))(2-x) (OPR(3))(2) (x = 0, 1, 2; OPR(3) = phosphine oxide) series of compounds: Uses as isomerization catalysts and stoichiometric and catalytic oxidants in organic chemistry.

摘要

Dioxo and dioxygen complexes of molybdenum have a diverse chemistry. They are of considerable and growing importance due to their catalytic applications and their role in biological systems. This dissertation describes the syntheses and reactivity studies on the MOCl₂(O)_x(O₂) _2−x(OPR₃)₂ (x = 0, 1, 2; OPR₃ = phosphine oxides) series of compounds.; The dioxo compound MOCl₂O₂(OPMePh₂) ₂, has been prepared and characterized. The use of this compound and its analogous species MOCl₂O₂(OPPh₃) ₂ as catalytic oxidants in organic chemistry have been investigated.; The synthesis of oxoperoxo compound MoCl₂O(O₂)(OPR) ₂ (OPR = OPMePh₂, OPPh₃) has been accomplished. They are characterized by their 1H and 31P NMR, and IR spectra, and by single crystal diffraction determination. Their abilities to isomerize some allylic alcohols are investigated, and a mechanism has been proposed based on 18O isotopic studies.; Compositional disorder with isostructural complexes MoCl₄(OPMePh ₂)₂, MOCl₃O(OPMePh₂)₂, and MoCl₂O₂(OPMePh₂)₂ was conducted as determined by X-ray single crystal diffraction. The nature of tincalconite has been reassessed.