Flash kinetics in liquefied noble gases: Studies of alkane activation and ligand dynamics at rhodium carbonyl centers, and a search for xenon-carbene adducts

Abstract

Chapter 1. A general introduction is given to place the subsequent chapters in context for the nonspecialist.Chapter 2. Results are presented from a low temperature infrared (IR) flash kinetic study of C-H bond activation via photoinduced reaction of Cp*Rh(CO) 2 (1) with linear and cyclic alkanes in liquid krypton and liquid xenon solution. No reaction was observed with methane; for all other hydrocarbons studied, the rate law supports fragmentation of the overall reaction into an alkane binding step followed by an oxidative addition step. Chapter 5. Results are presented from a picosecond pump-probe study designed to measure the impact of added xenon on the singlet-to-triplet intersystem crossing rates of diarylcarbenes. Within the error margins of the measurements, no effect of added xenon was observed. ii