Phosphine photolabilisation studies of (η5-C5H5)Fe(PPh3)(CO)-COR (R = Me, Ph, 2,6-C6H3F2) and (η5-C5Me5)Fe(PPh3)(CO)-COR (R = Me, 2,6-C6H3F2) utilising NMR, laser desorption FT ICR MS and photofragmentation voltammetry analysis
Aplin RT., Booth J., Compton RG., Davies SG., Jones S., McNally JP., Metzler MR., Watkins WC.
Photolysis of (η5-C5Me5)Fe(CO)(PPh3)COR (R = 2,6-C6H3F2, Me) leads to preferential loss of the phosphine ligand to form the corresponding alkyl species (η5-C5Me5)Fe(CO)(PPh3)R, while photolysis of (η5-C5H5)Fe(CO)(PPh3)COR (R = Me, Ph, 2,6-C6H3F2) leads to loss of CO to form (η5-C5H5)Fe(CO)(PPh3)R which subsequently undergoes rapid phosphine exchange. A mechanism for this process is proposed which is corroborated using photofragmentation voltammetry. Laser desorption mass spectrometry was also used as a tool to probe whether phosphine loss was the primary photochemical process.