Abstract
Three methods of obtaining time-resolved Fourier-Transform infrared (TR-FTIR) absorption spectra of transition metal carbonyl radicals in hexane are reported here. For the first method, CpM(CO) 2L and Cp*M(CO) 2L (M = Mo, W; L = CO, PR 3) radicals have been generated by photodissociation of the corresponding metal–metal bonded dimers. Radicals of formula M(CO) 4L (M = Mn, Re; L = CO, PR 3, AsPh 3, SbPh 3) and CpM(CO) n (M = Fe, Mo; n = 2, 3) have been produced via the second method which is halogen abstraction of the transition metal carbonyl halides using CpMo(CO) 3 radical. For the third method, fast radical ligand substitution kinetics has been exploited to generate CpMo(CO) 2PR 3 radicals from CpMo(CO) 3 in the presence of free phosphines. An assessment of the three methods with respect to TR-FTIR spectroscopic detection of radicals was also discussed.
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