Core-shell PdCu bimetallic colloidal nanoparticles in Sonogashira cross-coupling reaction: mechanistic insights into the catalyst mode of action

Drielly N Olekszyszen; Brunno L Albuquerque; Dagoberto de O Silva; Guilherme L Tripodi; Daniela C de Oliveira; Josiel B Domingos

doi:10.1039/c9nr09075d

Core-shell PdCu bimetallic colloidal nanoparticles in Sonogashira cross-coupling reaction: mechanistic insights into the catalyst mode of action

Nanoscale. 2020 Jan 14;12(2):1171-1179. doi: 10.1039/c9nr09075d. Epub 2019 Dec 18.

Authors

Drielly N Olekszyszen¹, Brunno L Albuquerque², Dagoberto de O Silva³, Guilherme L Tripodi⁴, Daniela C de Oliveira⁵, Josiel B Domingos³

Affiliations

¹ LaCBio - Laboratory of Biomimetic Catalysis, Department of Chemistry, Federal University of Santa Catarina, Campus Trindade, Florianópolis, SC 88040-900, Brazil. josiel.domingos@ufsc.br and Federal Institute of Paraná, Campus União da Vitória, PR 84600-000, Brazil.
² LaCBio - Laboratory of Biomimetic Catalysis, Department of Chemistry, Federal University of Santa Catarina, Campus Trindade, Florianópolis, SC 88040-900, Brazil. josiel.domingos@ufsc.br and LAMOCA, Institute of Chemistry, Federal University of Rio Grande do Sul, Porto Alegre, RS 91509-900, Brazil.
³ LaCBio - Laboratory of Biomimetic Catalysis, Department of Chemistry, Federal University of Santa Catarina, Campus Trindade, Florianópolis, SC 88040-900, Brazil. josiel.domingos@ufsc.br.
⁴ Institute for Molecules and Materials, Radboud University, Heyendaalseweg 135, 6525 AJ Nijmegen, The Netherlands.
⁵ Brazilian Synchrotron Light Laboratory, C. P. 6192, Campinas, SP 13083-970, Brazil.

PMID: 31850429
DOI: 10.1039/c9nr09075d

Abstract

Core-shell PdCu nanoparticles with different metal proportions were synthesized using a one-pot methodology and characterized by STEM, HRTEM, XANES and EXAFS analysis. The bimetallic nanoparticles were applied as catalysts in the Sonogashira cross-coupling reaction to investigate the mode of action of the PdCu in the reaction. The copper content directly influenced the generation of the cross-coupling product, shaping the performance of the catalyst. A quasi-homogeneous reaction pathway was evidenced by kinetics and poisoning experiments as well as XAS, HRTEM and HRMS analysis. These findings help to elucidate the mode of action of the PdCu nanocatalysts in the, as yet, unrevealed Sonogashira mechanism and the potential development of new nanocatalysts.