ChemPhysChem 2014-08-04

Following the azide-alkyne cycloaddition at the silica/solvent interface with sum frequency generation.

Zhiguo Li, Champika N Weeraman, Julianne M Gibbs-Davis

Index: ChemPhysChem 15(11) , 2247-51, (2014)

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Abstract

The Cu(I) -catalyzed 1,3-dipolar azide-alkyne cycloaddition (CuAAC) has arisen as one of the most useful chemical transformations for introducing complexity onto surfaces and materials owing to its functional-group tolerance and high yield. However, methods for monitoring such reactions in situ at the widely used silica/solvent interface are hampered by challenges associated with probing such buried interfaces. Using the surface-specific technique broadband sum frequency generation (SFG), we monitored the reaction of a benzyl azide monolayer in real time at the silica/methanol interface. A strong peak at 2096 cm(-1) assigned to the azides was observed for the first time by SFG. Using a cyano-substituted alkyne, the decrease of the azide peak and the increase of the cyano peak (2234 cm(-1) ) were probed simultaneously. From the kinetic analysis, the reaction order with respect to copper was determined to be 2.1, suggesting that CuAAC on the surface follows a similar mechanism as in solution. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.