Combining density functional theory and high resolution NC-AFM experiments, we have studied the on surface reaction mechanisms' responsible for the covalent dimerization of 4-iodobenzoic acid (IBA) organic molecules on the calcite (10.4), insulating surface. When annealed at 580 K, the Molecules assemble in one-dimensional chains of covalently bound dimers: The chains have a unique orientation and result from a complex set of processes, including a nominally rather. costly double dehalogenation reaction followed by dimerization. First, focusing on the latter two processes and using the nudged elastic band method, we analyze a number of possible mechanisms involving one and two molecules, and we isolate, the key aspects facilitating the reaction on calcite. Second, we find that the insulating surface plays an active role as a catalyst by identifying two relevant processes: one exhibiting an intermediate state of chemisorbed molecules after independent dehalogenations and a second, highly nontrivial exothermic reaction:, channel in which two iodine atoms "cooperate" to minimize the cost of their individual detachment from the molecules. Both processes have dramatically reduced energy barriers compared to all other mechanisms analyzed. The knowledge of the formation Mechanisms of a covalent assmebly. on insulators represents an important step toward the realization and control of structures that comhine the robustness of covalent architectures with their electronic decoupling from the insulating, substrate. This step has potentially important technological applications in nano- and molecular electronics.