Cooperative action for molecular debromination reaction on Cu(110)

Abstract

The metal-catalyzed coupling of halobenzene derivatives leading to biaryls and larger carbon-based structures is a fundamental reaction in chemical synthesis. 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 the 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 neighbouring complexes resulting in the formation of Cu coordinated BTD structures.