Linear-Structure Single-Atom Gold(I) Catalyst for Dehydrogenative Coupling of Organosilanes with Alcohols

A strategyfor the synthesisof a gold-basedsingle-atom catalyst(SAC) via a one-steproom temperaturereductionofAu(III)salt and stabilizationof Au(I) ions on nitrile-functionalizedgraphene(cyanographene;G-CN)is described.The graphene-supportedG(CN)-Aucatalystexhibitsa unique linear structureofthe Au(I) active sites promotinga multistepmode of action indehydrogenativecouplingof organosilaneswith alcoholsundermild reactionconditionsas provenby advancedXPS, XAFS,XANES,and EPR techniquesalong with DFT calculations.Thelinear structurebeing perfectlyaccessibletowardthe reactantmoleculesand the cyanographene-inducedcharge transferresultingin the exclusiveAu(I) valencestate contributeto the superiorefficiencyof the emergingtwo-dimensionalSAC. The developedG(CN)-AuSAC, despiteits low metal loading(ca. 0.6 wt %),appearto be the most efficientcatalystfor Si−H bond activationwith a turnoverfrequencyof up to 139,494h−1and highselectivities,significantlyovercomingall reportedhomogeneousgold catalysts.Moreover,it can be easily preparedin a multigrambatch scale, is recyclable,and works well toward more than 40 organosilanes.This work opens the door for applicationsof SACs witha linear structureof the active site for advancedcatalyticapplications.