The photodissociation dynamics of CpCo(CO)(2) was studied in a molecular beam using photofragment translational energy spectroscopy with 157 nm photoionization detection of the metallic products. At 532 and 355 nm excitation, the dominant one-photon channel involved loss of a single CO ligand producing CpCoCO. The product angular distributions were isotropic, and a large fraction of excess energy appeared as product vibrational excitation. Production of CpCO + 2CO resulted from two-photon absorption processes. The two-photon dissociation of mixtures containing CpCo(CO)(2) and H-2 at the orifice of a pulsed nozzle was used to produce a novel 16-electron unsaturated species, CpCoH2. Transition metal ligand exchange reactions, CpCoH2 + L) -> CpCoL + H-2 (L = propyne, propene, or ammonia), were studied under single-collision conditions for the first time. In all cases, ligand exchange occurred via 18-electron association complexes with lifetimes comparable to their rotational periods. Although ligand exchange reactions were not detected from CpCoH2 collisions with methane or propane (L = CH, or C3H8), a molecular beam containing CpCoCH4 was produced by photolysis of mixtures containing CpCo(CO)(2) and CH4.