Rhodium(i) complexes derived from tris(isopropyl)-azaphosphatrane-controlling the metal-ligand interplay

Proazaphosphatranes are intriguing ligand architectures comprising a bicyclic cage of flexible nature. They can undergo structural deformations due to transannulation while displaying modular electronic and steric properties. Herein, we report the synthesis and coordination chemistry of rhodium(i) complexes bearing a tris(isopropyl)-azaphosphatrane (TⁱPrAP) ligand. The molecular structure of the primary complex (1) revealed the insertion of the metal center into a P-N bond of the ligand. The addition of a Lewis acid, i.e., lithium chloride, promoted the dynamic behavior of the complex in the solution, which was studied by state-of-the-art NMR spectroscopy. Substituting the cyclooctadiene ligand at the metal center with triphenylphosphine or 2-pyridyldiphenylphosphine unveiled the adaptive nature of the TⁱPrAP backbone capable of switching its axial nitrogen from interacting with the phosphorus atom to coordinate the rhodium center. This led the entire ligand edifice to change its binding to rhodium from a bidentate to tridentate coordination. Altogether, our study shows that introducing a TⁱPrAP ligand allows for unique molecular control of the immediate environment of the metal center, opening perspectives in controlled bond activation and catalysis.