Part One. High valent oxo imido rhenium(VII) complexes: Mechanisms of their formation from azide and their use in catalytic oxidation of triethylsilane. Part Two. Single-site olefin polymerization: Kinetics and mechanistic insight from molecular weight distribution
Abstract
Catalysis is a central theme in inorganic research. Transition metal complexes are used to catalyze transformations that vary from olefin polymerization, group transfer, oxidation, reduction, metathesis, and many more. The types of mechanisms that these processes undergo are numerous. In this body of work, transformations that are paramount in the chemistry of two different transition metals will be discussed: rhenium and zirconium. High valent rhenium oxo and imido complexes catalyze oxygen atom transfer to a variety of substrates. Within this text is reported the synthesis of a cationic Re(VII) oxo imido complex from azide and its unusual mechanism of competing azide coordination modes (Chapter 2). This novel complex is then shown to catalyze the autoxidation of triethylsilane and the hydrosilylation of benzaldeyde. Under inert atmosphere, the complex transfers its oxo group to triethylsilane to afford silanol (Chapter 3). In chapters 4-7, the kinetics and mechanism of Group IV single-site olefin polymerization is introduced. A new method of globally analyzing multiple types of data simultaneously is presented with the promise of uncovering mechanistic detail otherwise overlooked (Chapter 5). Finally, the synthesis and initial kinetics of a zirconium bis(phenoxide) diamine polymerization catalyst is discussed (Chapters 6-7).
Degree
Ph.D.
Advisors
Abu-Omar, Purdue University.
Subject Area
Inorganic chemistry|Polymer chemistry
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