Bipyridinium and Phenanthrolinium Dications for Metal-Free Hydrodefluorination: Distinctive Carbon-Based Reactivity

The development of novel Lewis acids derived from bipyridinium and phenanthrolinium dications is reported. Calculations of Hydride Ion Affinity (HIA) values indicate high carbon-based Lewis acidity at the ortho and para positions. This arises in part from extensive LUMO delocalization across the aromatic backbones. Species [C₁₀ H₆ R₂ N₂ CH₂ CH₂ ]²⁺ (R=H [1 a]²⁺ , Me [1 f]²⁺ , tBu [1 g]²⁺ ), and [C₁₂ H₄ R₄ N₂ CH₂ CH₂ ]²⁺ (R=H [2 a]²⁺ , Me [2 b]²⁺ ) were prepared and evaluated for use in the initiation of hydrodefluorination (HDF) catalysis. Compound [2 a]²⁺ proved highly effective towards generating catalytically active silylium cations via Lewis acid-mediated hydride abstraction from silane. This enabled the HDF of a range of aryl- and alkyl- substituted sp³ (C-F) bonds under mild conditions. The protocol was also adapted to effect the deuterodefluorination of cis-2,4,6-(CF₃ )₃ C₆ H₉ . The dications are shown to act as hydride acceptors with the isolation of neutral species C₁₆ H₁₄ N₂ (3 a) and C₁₆ H₁₀ Me₄ N₂ (3 b) and monocationic species [C₁₄ H₁₃ N₂ ]⁺ ([4 a]⁺ ) and [C₁₈ H₂₁ N₂ ]+ ([4 b]⁺ ). Experimental and computational data provide further support that the dications are initiators in the generation of silylium cations.