The compounds (η 5 -C 5 H 5 )(OC) 2 Fe-SiH 2 R with R=H (1) and CH 3 (2) have been isolated in krypton or nitrogen matrices and subsequently detected by Raman spectroscopy, followed by a detailed vibrational analysis. To study the photochemistry of the iron silyl complexes 1 and 2, Raman spectra were also taken after UV irradiation. Resonance Raman spectroscopy enabled the detection of newly generated species in low concentrations. Due to the observed differences in the spectra, a reaction mechanism for the photochemical conversion of 1 and 2 in matrices is suggested. The experimental spectra of 1 are compared with the vibrational data of density functional calculations. These calculations propose a CO-loss product with a (Fe, H, Si) three-centre bond as a stable intermediate for the photochemical conversion of 1. Infrared measurements confirm the photochemical CO elimination.