On the photofragmentation of Fe(CO)5. I. Infrared and Mössbauer evidence for the formation of Fe(CO)4 in polymer matrices

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Abstract
Pentacarbonyliron sorbed in low density polyethylene (LDPE) or polytetrafluorethylene (PTFE) and irradiated with UV light has been studied by infrared and Mössbauer spectroscopies. The main photofragment reacts with the residual pentacarbonyliron leading to the formation of Fe2(CO)9. This reaction, plus the information obtained from infrared and Mössbauer spectra, suggest that the new species could be assigned as tetracarbonyliron Fe(CO)4 and tricarbonyliron Fe(CO)3. We have proved that molecules sorbed in a polymer matrix can be used as Mössbauer absorbers at low temperature. The polymer matrix allowed the isolation of otherwise unstable species: The high permeability of LDPE to gaseous carbon monoxide precludes the reformation of pentacarbonyliron molecules, thus excluding the ‘‘cage effect’’ observed in frozen gas matrices.