The temperature- and pressure-dependent kinetics of Co+(CH3Br)n (n = 0,1) + CH3Br are measured from 300 to 600 K and from 0.2 to 0.5 Torr. Results are interpreted using density functional calculations and modeled with statistical theory. In the n = 0 case, the associative product Co+(CH3Br) dominates with a rate constant between 5 and 30% of the collisional value, while a minor channel yields CoBr+ + CH3 with a rate constant increasing with temperature. 0K bond dissociation energies (BDE) are determined for Co+-Br (2.8 ± 0.1 eV) and Co+-CH3Br (2.4 ± 0.25 eV). Ligation of Co+ (i.e. n = 1) significantly increases the bimolecular reaction rate constant. CoBr+(CH3Br) + CH3 is formed and the reaction has a positive temperature dependence. Interestingly, this rate constant decreases with increasing pressure due to competition of the association channel. Ligation increases the (CH3Br)Co+-Br BDE (3.0 ± 0.1 eV) relative to Co+-Br, but decreases the (CH3Br)Co+-CH3Br BDE (1.95 ± 0.25) relative to Co+-CH3Br. Both bimolecular reactions proceed by a metal-insertion mechanism with a significantly submerged transition state that does not affect the kinetics. Instead, the endothermicity of the reaction is rate-limiting. Discussion about how energy, impact parameter, and angular momentum affect specific rate constants for dissociation to reactants, reaction to products, and association are presented.