Most reported examples of transition metal-mediated pericyclic reactions have been shown to proceed by nonpericyclic mechanisms. However, the conversion of Fe(CO)(4)-cyclobutenes to Fe(CO)(3)-butadienes and CO is thought to proceed through a mechanism involving an electrocyclic ring-opening step. We have examined this and possible alternative mechanisms for the parent Fe(CO)(4)-cyclobutene complex using hybrid HF-DFT calculations. In this system there is an inherent preference for a pathway that avoids metal-templated electrocyclic ring-opening, but the pericyclic pathway is predicted to dominate for more elaborate substrates and under certain experimental conditions.