Titanium dichloride was investigated as a potential catalyst for the bis-silylation reaction of ethylene with hexachlorodisilane. Ab initio electronic structure calculations at the restricted Hartree−Fock (RHF), density functional (DFT), second-order perturbation (MP2), and couple cluster (CCSD) levels of theory were used to find optimized structures, saddle points, and minimum-energy paths that connect them. The reaction was found to have a net zero barrier at the DFT, MP2, and CCSD levels of theory. Dynamic correlation is found to be important for this reaction.