New routes to Cu(l)/Cu nanocatalysts for the multicomponent click synthesis of 1,2,3-triazoles

An array of copper and copper–zinc based nanoparticles (NPs) have been fabricated employing a variety of polymeric capping agents. Analysis by TEM, XRPD and XPS suggests that by manipulating reagent, reductant and solvent conditions it is possible to achieve materials that are mono-/narrow disperse with mean particle sizes in the ≤10 nm regime. Oxidative stability in air is achieved for monometallic NPs using poly(methyl methacrylate) (PMMA) anti-agglomerant in conjunction with a variety of reducing conditions. In contrast, those encapsulated by either poly(1-vinylpyrrolidin-2-one) (PVP) or poly(4-vinylpyridine) (PVPy) rapidly show Cu2O formation, with all data suggesting progressive oxidation from Cu to Cu@Cu2O core–shell structure and finally Cu2O. Bimetallic copper–zinc systems, reveal metal segregation and the formation of Cu2O and ZnO. Catalysts have been screened in the synthesis of 1,2,3-triazoles through multicomponent azide–alkyne 1,3-dipolar cycloaddition. Whereas PMMA- and PVPy-coating results in reduced catalytic activity, those protected by PVP are highly active, with quantitative triazole syntheses achieved at room temperature and with catalyst loadings of 0.03 mol% metal for Cu and CuZn systems prepared using NaH2PO2, N2H4 or NaBH4 reductants.This work was generously supported by the Spanish Ministerio de Ciencia e Innovación (MICINN; CTQ2007-65218 and Consolider Ingenio 2010-CSD2007-00006), the Generalitat Valenciana (GV; PROMETEO/2009/039), and FEDER. Y. M. and B. R. K. thank the ISO of the Universidad de Alicante, the UK EPSRC and the University of Cambridge for grants