Department of Chemistry, University of Idaho, Moscow, Idaho 83844-2343, USA.
Appl Spectrosc. 2010 Aug;64(8):907-11. doi: 10.1366/000370210792081019.
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 approximately 20 ms at 25 degrees C and approximately 70 ms at 10 degrees C. This intermediate transformed into a longer-lived (approximately 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.
在 CpCo(CO)(2) 与亚硝酰氯反应过程中，通过将快速混合停流装置与具有 5 ms 时间分辨率的超快速扫描傅里叶变换红外 (FT-IR) 光谱仪相连接，测量了全范围中红外光谱。该光谱仪的数据采集硬件的更改现在允许在不中断的情况下收集超过 2000 个光谱的序列。在 CpCo(CO)(2) 与亚硝酰氯反应的前 500 ms 期间，观察到两种瞬态物种。观察到的寿命最短的物种 CpCo(CO)(2)(NO)，在 25°C 时半衰期约为 20 ms，在 10°C 时半衰期约为 70 ms。该中间体转化为寿命更长（约 0.5 s）的中间体 CpCo(NO)Cl。虽然不能排除它们存在的可能性，但未观察到具有一个 CO 和一个 NO 配体的潜在中间物种，如 CpCo(CO)(NO) 和 CpCo(CO)(NO)Cl。
