Scope and Mechanism of Cooperativity at the Intersection of Organometallic and Supramolecular Catalysis

The scope and mechanism of the microenvironment-catalyzed C­(sp3)−C­(sp3) reductive elimination from transition metal complexes [Au­(III), Pt­(IV)] is explored. Experiments detailing the effect of structural perturbation of neutral and anionic spectator ligands, reactive alkyl ligands, solvent, and catalyst structure are disclosed. Indirect evidence for a coordinatively unsaturated encapsulated cationic intermediate is garnered via observation of several inactive donor-arrested inclusion complexes, including a crystallographically characterized encapsulated Au­(III) cation. Finally, based on stoichiometric experiments under catalytically relevant conditions, a detailed mechanism is outlined for the dual supramolecular and platinum-catalyzed C–C coupling between methyl iodide and tetramethyltin. Determination of major platinum species present under catalytic conditions and subsequent investigation of their chemistry reveals an unexpected interplay between cis–trans isomerism and the supramolecular catalyst in a Pt­(II)/Pt­(IV) cycle, as well as several off-cycle reactions.