Phosphine photolabilisation studies of (#eta#~5-C_5H_5)Fe(PPh_3)(CO)-COR (R = Me, Ph, 2,6-C_6H_3F_2) and (#eta#~5-C_5Me_5)Fe(PPh_3)(CO)-COR (R = Me, 2,6-C_6H_3F_2) utilising NMR, laser desorption FT ICR MS and photofragmentation voltammetry analysis

摘要

Photolysis of (#eta#~5-C_5Me_5)Fe(CO)(PPh_3)COR (R = 2.6-C_6H_3F_2, Me) leads to preferential loss of the phosphine ligand to form the corresponding alkyl species (#eta#~5-C_5Me_5)Fe(CO)(PPh_3)R, while photolysis of (#eta#~5-C_5H_5)Fe(CO)(PPh_3)COR (R = Me, Ph, 2,6-C_6H_3F_2) leads to loss of CO to form (#eta#~5-C_5H_5)Fe(CO)(PPh_3)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.