Boron, Aluminum,and Gallium Fluorides as Catalystsfor the Defluorofunctionalization of Electron-Deficient Arenes: TheRole of NaBAr^F₄ Promoters

A series of boron, aluminum, and gallium difluoride complexes [{(ArNCMe)₂CH}­MF₂] (M = B, Al, Ga) are reported as catalysts for the defluorofunctionalization of electron-deficient arenes. Thiodefluorination reactions between TMS–SPh and poly­(fluorinated aromatics) proceed under forcing conditions. Evidence is presented for the fluoride entering the catalytic cycle through a metathesis reaction with TMS–SPh to form metal thiolate intermediates, e.g., [{(ArNCMe)₂CH}­MF­(SPh)], which are then nucleophiles for addition to the aromatic substrate, likely through a concerted S_NAr mechanism. Attempts to expand the scope of reactivity to include the hydrodefluorination of electron-deficient arenes met with limited success. Activity could, however, be recovered through the addition of NaBAr^F₄ as a catalytic additive (Ar^F = 3,5-C₆H₃(CF₃)₂). NMR titrations suggest that NaBAr^F₄ is capable of coordinating with aluminum and gallium fluoride complexes, most likely through weak M–F---Na interactions (M = Al, Ga), and can play a role in lowering the barrier of metathesis between [{(ArNCMe)₂CH}­MF₂] and Et₃SiH to form the group 13 hydrido fluoride [{(ArNCMe)₂CH}­M­(H)­F], facilitating catalytic turnover. DFT calculations indicate that this weak interaction leads to a polarization of the M–F bond. The discovery of this additive effect has potentially broad implications in developing new reactivity and applications of thermodynamically stable metal fluorides.