The perfluoro- and perprotiopentaphenylboroles 1 and 2 react with dihydrogen to effect H-H bond cleavage and formation of boracyclopentene products. The mechanism of this reaction has been studied experimentally through evaluation of the kinetic properties of the slower reaction between 2 and H-2. The reaction is first-order in both [borole] and [H-2] with activation parameters of Delta H-double dagger = 34(8) kJ/mol and Delta S-double dagger = -146(25) J mol(-1) K-1. A minimal kinetic isotope effect of 1.10(5) was observed, suggesting an asynchronous geometry for H-H cleavage in the rate-limiting transition state. To explain the stereochemistry of the observed products, a ring-opening/ring-dosing mechanism is proposed and supported by the separate synthesis of a proposed intermediate and its observed conversion to product. Furthermore, extensive DFT mapping of the reaction mechanism supports the plausibility of this proposal. The study illustrates a new mechanism for the activation of H-2 by a strong main group Lewis acid in the absence of an external base, a process driven in part by the antiaromaticity of the borole rings in 1 and 2.