Metal-benzene complexes of the form M(benzene)(n) (M = Ti, V, Fe, Co, Ni) are produced in the gas-phase environment of a molecular beam by laser vaporization in a pulsed nozzle cluster source. These complexes are photoionized with an ArF excimer laser, producing the corresponding cations. The respective mono- and dibenzene complex ions are isolated in an ion-trap mass spectrometer and studied with infrared resonance enhanced multiple-photon dissociation (IR-REMPD) spectroscopy using a tunable free electron laser. Photodissociation of all complexes occurs by the elimination of intact neutral benzene molecules, and this process is enhanced on resonances in the vibrational spectrum, making it possible to measure vibrational spectroscopy for size-selected complexes. Vibrational bands in the 600-1700 cm(-1) region are characteristic of the benzene molecular moiety with systematic shifts caused by the metal bonding. The spectra in this solvent-free environment exhibit periodic trends in band shifts and intensities relative to the free benzene molecule that varies with the metal. Density functional theory calculations are employed to investigate the structures, energetics, and vibrational frequencies of these complexes. The comparison between experiment and theory provides fascinating new insight into the bonding in these prototypical organometallic complexes.