This investigation combines theoretical results and experimental data to elucidate the main kinetic and mechanism for the ring opening metathesis polymerization of norbornene by means of the [RuCl2(PPh3)(2)(piperidine)] complex as catalyst initiator. Structural species were defined and a kinetic profile of the entire reaction is depicted. The determined mechanism showed an associative reaction between the [RuCl2(PPh3)(2)(piperidine)] complex initiator and ethyl diazoacetate as the first step, resulting in a metal-carbene species. This species loses one triphenylphosphine molecule (PPh3) and the global rate-determining step is associated with a removal of the second PPh3 molecule due to an electronic trans-synergism between piperidine and this PPh3 molecule. Entropic factors are crucial to the spontaneity observed for the dissociation of both PPh3 ligands. The step following the rate-determining one is associated with the binding of a norbornene molecule and a similar trans-synergism between this monomer and piperidine activates the catalysis. This electronic effect maintains the system in a very important conformation along the catalytic chain. (C) 2015 Elsevier B.V. All rights reserved.