Electronic absorption and resonance Raman spectral studies reveal that adding the benzoyl group to a cyclopentadienyl ring of osmocene (Oc) causes a significant perturbation of electronic properties. The lowest energy electronic excited states in Oc, which are primarily ligand field in nature ligand, acquire metal-to-ligand charge transfer (MLCT) character in benzoylosmocene (BOc). Both Oc and BOc are relatively photoinert (disappearance quantum yield <10^-3) in methanol. Irradiating the metallocenes in neat ethyl 2-cyanoacrylate (CA) initiates the anionic polymerization of the electrophilic monomer. This photoinitated process results from the population of a charge-transfer-to-solvent (metallocenes --> CA) excited state, which generates the monomer radical anion as the actual initiating species. Comparison of the present results for Oc and BOc with those reported previously for the corresponding ferrocene and ruthenocene compounds reveals some interesting similarities and differences in the excited state behavior of this homologous family of group 8 metallocenes.