Efficient Lanthanide Catalyzed Debromination and Oligomeric Length-Controlled Ullmann Coupling of Aryl Halides

Lanthanide elements play a vital role in a broad range of high-tech applications, and there is an increasing interest in their catalytic activity, particularly in organo-metallics. However, their catalytic role on surfaces remains unexplored. Here, we present a scanning tunneling microscopy and density functional theory study of the debromination, contacting, and coupling of dibromine terphenyl species with Dy (f-block element) and Ag (d-block element) adatoms, respectively. We show that Dy debrominates the targeted species more efficiently than Ag adatoms at room temperature, promoting the formation of unprecedented C-Dy-C organo-metallic supramolecules versus C-Ag-C parallel chains for the Ag case. DFT calculations corroborate our results showing an almost spontaneous debromination process with Dy compared to Ag. Upon annealing, for samples containing Dy, the formation of C-Ag-C organometallic bonds and concomitant C-C coupling is inhibited, giving rise to a self-assembly of debrominated monomers, showing only a minority number of covalent dimes species. For samples without Dy covalent chains of irregular length are promoted. Our studies open new avenues for using lanthanide elements as efficient dehalogenation catalysts. Furthermore, we illustrate their potential as inhibitors of uncontrolled C-C coupling reactions, of great relevance for fine-tuning the length of polymeric compounds.
Funding Agencies|EC FP7-PEOPLE-COFUND AMAROUT II program; Spanish Ramon and Cajal Program [RYC-2012-11133]; Spanish Ministerio de Economia y Competitividad [FIS 2013-40667-P, FIS 2015-67287-P]; Comunidad de Madrid (projects MAD2D, NANOFRONTMAG) [52013/MT-2850]; IMDEA Foundation