Infrared spectroscopy and kinetics of short-lived organometallic intermediates

Abstract

The first part of this thesis focused on time-resolved step-scan Fourier-Transform infrared (TR-s2-FTIR) spectroscopy of transition-metal carbonyl radicals. The aim was to obtain the TR-s2-FTIR spectroscopic data of these radicals by using three different methods, namely, (1) 532nm dissociation of metal-metal bond, (2) abstraction of hydrogen, halogen or methyl from monomeric transition metal carbonyl species, and (3) fast radical ligand substitution. The second part of this thesis focused on the FTIR spectroscopy of iron carbonyl intermediates in isomerization of allylic alcohols. The aim was to obtain evidence to support the p-allyl mechanism of the isomerization of allylic alcohols by making the direct observation of the intermediates involved in the catalytic cycle. The final part of this study focused on the kinetics of methyl abstraction from CpFe(CO)2Me using benzyl radical clock. The aim was to develop simple methods of conducting the quantitative measurements of methyl transfer processes.