TR-FTIR absorption spectroscopy of transition metal carbonyl radicals generated by photodissociation of metal-metal bonds, by halogen abstraction or by radical ligand substitution |
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| Authors: | Thiam Seong Chong |
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| Institution: | Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore |
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| 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, PR3) radicals have been generated by photodissociation of the corresponding metal-metal bonded dimers. Radicals of formula M(CO)4L (M = Mn, Re; L = CO, PR3, AsPh3, SbPh3) 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)2PR3 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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| Keywords: | TR-FTIR radical spectra Metal-metal bond dissociation Halide abstraction Ligand substitution kinetics |
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