The designs, syntheses, and applications of well-defined, single component group VIII olefin metathesis catalysts

Citation

Nguyen, SonBinh TheBao (1995) The designs, syntheses, and applications of well-defined, single component group VIII olefin metathesis catalysts. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/1BVB-S189. https://resolver.caltech.edu/CaltechETD:etd-09282005-160712

Abstract

NOTE: Text or symbols not renderable in plain ASCII are indicated by [...]. Abstract is included in .pdf document. This thesis reports the synthesis and reactivity studies of a series of [...] complexes (X is an anionic ligand, L represents a neutral, two-electron donor ligand, M is either Ru or Os, and CHR represents a carbene moiety). These complexes are olefin metathesis catalysts and is remarkable in their stability toward a variety of functional groups, including protic species such as water and acid. Chapter 2 describes the synthesis, stability, and mechanism of formation of the forementioned [...] catalysts from a strained 3,3-disubstituted cyclopropene. Their metathesis activities as functions of the anionic ligands and the metal center will be discussed together with the mechanism of cyclopropene-vinylcarbene rearrangement at Group VIII metal centers . In chapter 3 and chapter 4, the modification of the metathesis activity of these catalysts as functions of the ancillary phosphine ligands and the carbene substituents, respectively, will be presented. Chapter 5 describes the applications of this new catalyst system in the self metathesis and ethenolysis of oleic acid and its methyl ester. The acyclic diene metathesis polymerization and polyolefin depolymerization reactions catalyzed by these new catalysts are the subjects of chapter 6. Chapter 7 reports the results of resin-immobilization experiments and Chapter 8 is a collection of the author's personal impressions of the development in this area of chemistry over the last decade.

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