Catalysis in a porous molecular capsule: Activation by regulated access to sixty metal centers spanning a truncated icosahedron

The 30 cationic {Mo ^V ₂O ₄(acetate)} ⁺ units linking 12 negatively charged pentagonal "ligands," {(Mo ^VI)Mo ^VI ₅O ₂₁(H ₂O) ₆} ^6- of the porous metal-oxide capsule, [{Mo ^VI ₆O ₂₁(H ₂O) ₆} ₁₂{Mo ^V ₂O ₄(acetate)} ₃₀] ^42- provide active sites for catalytic transformations of organic "guests". This is demonstrated using a well-behaved model reaction, the fully reversible cleavage and formation of methyl tert-butyl ether (MTBE) under mild conditions in water. Five independent lines of evidence demonstrate that reactions of the MTBE guests occur in the ca. 6 × 10 ³ Å ³ interior of the spherical capsule. The Mo atoms of the {Mo ^V ₂O ₄(acetate)} ⁺ linkers - spanning an ca. 3-nm truncated icosahedron - are sterically accessible to substrate, and controlled removal of their internally bound acetate ligands generates catalytically active {Mo ^V ₂O ₄(H ₂O) ₂} ²⁺ units with labile water ligands, and Lewis- and Brønsted-acid properties. The activity of these units is demonstrating by kinetic data that reveal a first-order dependence of MTBE cleavage rates on the number of acetate-free {Mo ^V ₂O ₄(H ₂O) ₂} ²⁺ linkers. DFT calculations point to a pathway involving both Mo(V) centers, and the intermediacy of isobutene in both forward and reverse reactions. A plausible catalytic cycle - satisfying microscopic reversibility - is supported by activation parameters for MTBE cleavage, deuterium and oxygen-18 labeling studies, and by reactions of deliberately added isobutene and of a water-soluble isobutene analog. More generally, pore-restricted encapsulation, ligand-regulated access to multiple structurally integral metal-centers, and options for modifying the microenvironment within this new type of nanoreactor, suggest numerous additional transformations of organic substrates by this and related molybdenum-oxide based capsules.