Reactivity of coordinatively unsaturated organometallic species in the gas phase and in solution.

摘要

Our application of the technique of infrared flash-kinetic spectroscopy to organometallic chemistry is laced in the context of recent work. The advantages and drawbacks of the CO-laser-based system used in these experiments relative to other infrared detection sources are weighed. The details of the CO laser transient IR spectrometer are given. We focus on the operation of the CO laser, a homebuilt instrument. The means of photolysis, detection, and data analysis are also described. We offer some advice on optimization of transient signal quality. The room-temperature flash-kinetic spectroscopy of CpCo(CO)(sub 2) in the gas phase and in organic solution is investigated. The primary observed photoproduct is the monocarbonyl CpCo(CO). We examine the gas-phase flash-kinetic spectroscopy of CpRh(CO)(sub 2). Again, the primary observed photoproduct is a monocarbonyl, CpRh(CO). This molecule is highly reactive, combining with CO at a frequency close to the collision rate. The photochemistry of Cp(asterisk)Rh(CO)(sub 2) in liquid krypton is probed. Reaction between an initially-formed monocarbonyl intermediate and the alkanes cyclohexane and neopentane is noted, yielding C-H activation products. 146 refs., 43 figs., 14 tabs.