MOF-Triggered Synthesis of Subnanometer Ag<sup>0</sup><sub>2</sub> Clusters and Fe<sup>3+</sup> Single Atoms: Heterogenization Led to Efficient and Synergetic One-Pot Catalytic Reactions
Estefanía Tiburcio, Yongkun Zheng, Cristina Bilanin, Juan Carlos Hernández‐Garrido, Alejandro Vidal‐Moya, Judit Oliver–Meseguer, Nuria Martín, Marta Mon, Jesús Ferrando–Soria, Donatella Armentano, Antonio Leyva‐Pérez, Emilio Pardo
Abstract
High Resolution Image Download MS PowerPoint Slide The combination of well-defined Fe 3+ isolated single-metal atoms and Ag 2 subnanometer metal clusters within the channels of a metal–organic framework (MOF) is reported and characterized by single-crystal X-ray diffraction for the first time. The resulting hybrid material, with the formula [Ag 0 2 (Ag 0 ) 1.34 Fe III 0.66 ]@Na I 2 {Ni II 4 [Cu II 2 (Me 3 mpba) 2 ] 3 }·63H 2 O ( Fe 3+ Ag 0 2 @MOF ), is capable of catalyzing the unprecedented direct conversion of styrene to phenylacetylene in one pot. In particular, Fe 3+ Ag 0 2 @MOF ─which can easily be obtained in a gram scale─exhibits superior catalytic activity for the TEMPO-free oxidative cross-coupling of styrenes with phenyl sulfone to give vinyl sulfones in yields up to >99%, which are ultimately transformed, in situ, to the corresponding phenylacetylene product. The results presented here constitute a paradigmatic example of how the synthesis of different metal species in well-defined solid catalysts, combined with speciation of the true metal catalyst of an organic reaction in solution, allows the design of a new challenging reaction.