MOF-Triggered Synthesis of Subnanometer Ag Clusters and Fe Single Atoms: Heterogenization Led to Efficient and Synergetic One-Pot Catalytic Reactions.

The combination of well-defined Fe isolated single-metal atoms and Ag 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(Ag)Fe]@Na{Ni[Cu(Mempba)]}·63HO (), is capable of catalyzing the unprecedented direct conversion of styrene to phenylacetylene in one pot. In particular, ─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.