Stopped-Flow Ultra-Rapid-Scanning Fourier Transform Infrared Spectroscopy on the Millisecond Time Scale

Abstract

Full-range mid-infrared spectra were measured during the reaction of CpCo(CO)2 with nitrosyl chloride by interfacing a rapid-mixing stopped-flow device with an ultra-rapid-scanning Fourier transform infrared (FT-IR) spectrometer having a temporal resolution of 5 ms. Changes to the data acquisition hardware of this spectrometer now allow a sequence of well over 2000 spectra to be collected without interruption. Two transient species were observed spectroscopically during the first 500 ms of the reaction of CpCo(CO)2 with nitrosyl chloride. The shortest-lived species that was observed, [CpCo(CO)2(NO)]+, had a half-life of ∼20 ms at 25 °C and ∼70 ms at 10 °C. This intermediate transformed into a longer-lived (∼0.5 s) intermediate, CpCo(NO)Cl. Potential intermediate species with one CO and one NO ligand, such as [CpCo(CO)(NO)]+ and CpCo(CO)(NO)Cl, were not observed, although the possibility that they exist cannot be ruled out.