Nucleophilic Reactivity at a ═CH Arm of a Lutidine-Based CNC/Rh System: Unusual Alkyne and CO₂ Activation

Reaction of an amido pincer complex [(CNC)*Rh(CO)] (1) (CNC* is the deprotonated form of CNC) with carbon dioxide gave a neutral complex [(CNC-CO₂)^Mes*Rh(CO)] (2), which is the result of a C-C bond-forming reaction between the deprotonated arm of the CNC* ligand and CO₂. The molecular structure of 2 showed a zwitterionic complex, where the CO₂ moiety is covalently connected to the former ═CH arm of the CNC* pincer ligand. The unusual structure of 1 allowed us to explore the reactivity of the CO₂ moiety with selected primary amines RNH₂ (benzylamine and ammonia), which afforded cationic complexes [(CNC)^MesRh(CO)][HRNC(O)O] (R = Bz (3), H (4)). Compounds 3 and 4 are the result of a C-N coupling between the incoming amine and the CO₂ fragment covalently connected to the pincer ligand in 2, a process that involves protonation of the "CH-CO₂" fragment in 2 from the respective amines. Once revealed the nucleophilic character of the ═CH fragment in 1, we explored its reactivity with alkynes, a study that enlightened a novel reactivity trend in alkyne activation. Reaction of 1 with terminal alkynes RC≡CH (R = Ph, 2-py, 4-C₆H₄-CF₃) yielded neutral complexes [(CNC-CH═CHR)^Mes*Rh(CO)] (R = Ph (5), 2-py (6), 4-C₆H₄-CF₃ (7)) in good yields. Deuterium labeling experiments with PhC≡CD confirmed that complex 5 is the product of a formal insertion of the alkyne into the C(sp²)-H bond of the deprotonated arm in 1. This structural proposal was further confirmed by the X-ray molecular structure of phenyl complex 5, which showed the alkyne covalently linked to the pincer ligand. Besides, this novel transformation was analyzed by DFT methods and showed a metal-ligand cooperative mechanism, based on the initial electrophilic attack of the alkyne to the ═CH arm of the CNC^Mes* ligand (making a new C-C bond) followed by the action of a protic base (HN(SiMe₃)₂), which is able to perform a proton rearrangement that leads to the final product 5.