Raman spectroscopy was performed on some metallosilanes, chelat-substituted tetracarbonyl complexes, and trans-[CpFe(CO)₂]₂ (Cp = η⁵-C₅H₅). The vibrational spectra of different silyl complexes are discussed by means of normal coordinate calculations for the M-SiH₃ fragment. The calculated force fields and potential energy distributions demonstrate the complicated vibrational behaviour of the metallosilanes as well as the influence of the remaining ligands. A complete normal coordinate analysis (NCA) was carried out for Cp(CO)₂Fe-SiH₃, including the whole Cp ligand. Matrix isolation Raman spectroscopy was used to study the photochemistry of carbonyl metal silyl complexes. Results of the irradiation experiments of Cp(CO)₂Fe-SiH₂(CH₃) at 20 K isolated in a krypton matrix are discussed. High resolution low-temperature Raman spectra of polycrystalline cis-(L-L)M(CO)₄ complexes show characteristic v(CO) splitting patterns interpreted by crystal effects. Results are presented from factor group analyses of (dppm)Mo(CO)₄ [dppm = bis(diphenylphosphino)methane] and (dppe)Cr(CO)₄ [dppe = bis(diphenylphosphino)ethane]. Resonance Raman studies of polycrystalline and matrix isolated trans-[CpFe(CO)₂]₂ leads to an assignment of the characteristic modes and the detection of a triply bridged Cp₂Fe₂(CO)₃ photogenerated intermediate.