| Summary: | Mass spectrometry, ion spectroscopy, NMR and quantum-chemical calculations are commonly combined to study the structures, properties and reactivity of intermediates in metal- catalyzed reactions. However, our ability to identify the main species present in solution by electrospray ionization mass spectrometry (ESI-MS) and to confirm whether these species are indeed reactive intermediates involved in the study reactions remains limited. Thus, we developed a new method combining isotope labeling with kinetic data extraction for the identification and analysis of intermediates in reaction mixtures termed delayed reactant labeling (DRL). Accordingly, this thesis is divided into 5 Chapters. Chapter 1 gives an overview of ESI-MS as a tool for studying the mechanisms of metal-catalyzed reactions, focusing on gold chemistry. Chapter 2 describes the experimental (ESI-MS, ion spectroscopy and gas chromatography) and theoretical (DFT) methods used in this thesis and the corresponding instrumentation. Chapter 3 details the development of the delayed reactant labeling (DRL) as a technique for studying reaction kinetics by mass spectrometry and examples how it was used to investigate problems in the following chapter. Chapter 4, shows that a Au(I) complex can act as a strong base in a solution containing water...
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