Tris(quinolin-8-yl)phosphite, P(Oquin)(3), promotes the dehydrogenation of H3N center dot BH3 (AB) and the transfer hydrogenation of azoarenes using ammonia borane (AB) as H-2 source. The metal-free reduction of azoarenes proceeds under mild reaction conditions upon which several diphenylhydrazine derivatives are obtained in high yields. The reactivity of P(Oquin)(3) toward AB was evaluated through NMR in situ tests. The rate of the reaction, activation parameters, deuterium kinetic isotope effect (DKIE) and linear-free energy relationship were investigated. Such mechanistic and kinetic studies suggest that P(Oquin)(3) is a precatalyst and that AB is likely involved in more than one stage of the reaction pathway. Furthermore, the kinetic data indicate that the reaction proceeds through an ordered transition state, possibly associative.