Development of a Stopped-Flow Ultra-Rapid-Scanning Fourier Transform Infrared Spectrometer and its Application for Kinetic and Mechanistic Studies of Inorganic Compounds

This dissertation describes the development of a stopped-flow ultra-rapid-scanning Fourier transform infrared spectrometer and its application for studying the kinetics and mechanisms of rapid chemical reactions. The instrument can consistently measure 200 full-range mid-IR (4000--800 cm-1) spectra per second which meshes seamlessly with the ∼10ms mixing time of a stopped-flow instrument. With recent upgrades this instrument is capable of measuring 1000 full-range mid-IR spectra per second. This instrument is still a prototype and with a faster mixing device one can exploit the faster rate of data collection. The secondary focus describes mechanistic studies of transition metal carbonyls with nitrosyl chloride.;Chapter 1 describes the basics and development of the stopped-flow rapid-scanning Fourier transform infrared spectrometer and its advantages over other stopped flow IR spectrometers. Comparisons are drawn between other stopped-flow FT-IR spectrometers with an emphasis on the rate of data acquisition, the spectral range in which data is collected and the efficiency of the spectrometer.;Chapter 2 describes the oxidative elimination reaction of Fe(CO) 3(PPh3)2 with I2 and chapter 3 describes the mechanism for bridge breaking reaction of [Rh(CO)2Cl] 2 with PPh3.;Chapter 4 briefly discuss the important of metal-nitrosyl chemistry and the purpose for studying the kinetics and mechanism for the reactions of metal carbonyl complexes with nitric oxide. Mechanistic data for the reactions of CpCo(CO)2, Ru(CO)3(PPh3)2 and CpCr(CO)2(NO) with nitrosyl chloride are described in Chapters 4. Intermediates with life-times as short as ∼50 milliseconds were observed, and in some cases never before observed species were seen. Furthermore these studies provided preliminary evidence that these reactions follow an S N2 type mechanism.;Chapter 7 discusses future studies, improvements to the stopped-flow rapid mixing device and a recently acquired Global Works (U.S.A. Olis) kinetic software package.