We have previously proposed that the Hg(arene)(2)(GaCl4)(2) catalyzed H/D exchange reaction of C6D6 with arenes occurs via an electrophilic aromatic substitution reaction in which the coordinated arene protonates the C6D6. To investigate this mechanism, the kinetics of the Hg(C6H5Me)(2)(GaCl4)(2) catalyzed H/D exchange reaction Of C6D6 with naphthalene has been studied. Separate second-order rate constants were determined for the 1- and 2-positions on naphthalene; that is, the initial rate of H/D exchange = k(1i)[Hg][C-H-1] + k(2i)[Hg][C-H-2]. The ratio of k(1i)/k(2i) ranges from 11 to 2.5 over the temperature range studied, commensurate with the proposed electrophilic aromatic substitution reaction. Observation of the reactions over an extended time period shows that the rates change with time, until they again reach a new and constant second-order kinetics regime. The overall form of the rate equation is unchanged: final rate = k(1f)[Hg](C-H-1] + k(2f)[Hg][C-H-2]. This change in the H/D exchange is accompanied by ligand exchange between Hg(C6D6)(2)(GaCl4)(2) and naphthalene to give Hg(C10H8)(2)(GaCl4)(2), that has been characterized by C-13 CPMAS NMR and UV-visible spectroscopy. The activation parameters for the ligand exchange may be determined and are indicative of a dissociative reaction and are consistent with our previously calculated bond dissociation for Hg(C6H6)(2)(AlCl4)(2). The initial Hg(arene)(2)(GaCl4)(2) catalyzed reaction of naphthalene with C6D6 involves the deuteration of naphthalene by coordinated C6D6; however, as ligand exchange progresses, the pathway for H/D exchange changes to where the protonation Of C6D6 by coordinated naphthalene dominates. The site selectivity for the H/D exchange is initially due to the electrophilic aromatic substitution of naphthalene. As ligand exchange occurs, this selectivity is controlled by the activation of the naphthalene C-H bonds by mercury.