MOF-Triggered Synthesis of Subnanometer Ag(0)(2) Clusters and Fe(3+) Single Atoms: Heterogenization Led to Efficient and Synergetic One-Pot Catalytic Reactions

[Image: see text] 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.