Cooperative sction for molecular debromination reaction on Cu(110)

Copper is the paradigmatic catalyzer of the Ullmann cross-coupling reaction. Despite this, its role in the reaction is still under debate. Here, we shed light on the mechanistic steps of debromination, characterizing a prototypical molecule, namely 4,7-dibromobenzo[c]-1,2,5-thiadiazole (2Br-BTD), deposited on a Cu(110) surface. By means of scanning probe techniques and first principle calculations, we demonstrate the oxidative addition of Cu atoms leading to a -C-Cu-Br metal-organic complex. The scission of the strongly bound bromine atoms requires the cooperative action of neighboring complexes resulting in the formation of Cu-coordinated BTD structures.All authors acknowledge the economic support of the Spanish Ministry of Economy, Industry and Competitiveness (MINECO Grant number MAT2016-78293-C6-5-R and FIS2016-75862-P). A.B. acknowledges Vicerrectorado de Investigación of the University of the Basque Country (UPV/EHU) for the PhD fellowship (2016)Peer Reviewe