Entrapment of THF-Stabilized Iridacyclic Ir^III Silylenes from Double H-Si Bond Activation and H₂ Elimination

The reaction of H₃ SiR (R=Ph, nBu) with cationic η₅ -C₅ Me₅ - (Cp*) and benzo[h]quinolinyl-based iridacycle [1 b]⁺ gives rise to new [(IrH)→SiRH₂ ]⁺ adducts. In the presence of THF these adducts readily undergo elimination of H₂ gas at subambient temperature to form THF-stabilized metallacyclic Ir^III silylene complexes, which were characterized in situ by NMR spectroscopy, trapped in minute amounts by reactive crystallization, and structurally characterized by XRD. Theoretical investigations (static DFT-D reaction-energy profiling, ETS-NOCV) support the promoting role of THF in the H₂ elimination step and the consolidation of the Ir-to-Si interaction in the spontaneous (ΔG<0) formation of Ir silylenes in the presence of THF. Mechanistic insights indicate that the Ir silylene species arising from the [1 b]⁺ /phenylsilane system are relevant catalytic species in the hydrodefluorination of fluoroalkanes.