Binary-encoded poly(alkoxyamine amide)s were prepared by oligomer ligation. These polymers contain digital sequences based on two monomers defined as 0 and 1 bits. A library of oligomers containing all possible dyads 00, 01, 10 and 11 was prepared and used to construct long coded sequences.

The reaction of H SiR (R=Ph, nBu) with cationic η -C Me - (Cp*) and benzo[h]quinolinyl-based iridacycle [1 b] gives rise to new [(IrH)→SiRH ] adducts. In the presence of THF these adducts readily undergo elimination of H gas at subambient temperature to form THF-stabilized metallacyclic Ir 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 H 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.