Reactivity of a Pacman Chlorophosphane Toward Ammonia and Azide: Formation and Characterization of a Diamino‐ and a Diazidophosphane

The halide substitution reactions of the Pacman chlorophosphane Pac(PCl) 2 with NH 3 and AgN 3 provide straightforward access to the corresponding diamine Pac(PNH 2 ) 2 and diazide Pac(PN 3 ) 2 , respectively, both of which were isolated in good yields. Multinuclear NMR spectroscopy, including 1 H, 31 P, and two‐dimensional 1 H– 31 P/ 1 H– 15 N HMBC experiments, revealed that both compounds exist as mixtures of endo–exo and exo–exo isomers in solution and enabled their unambiguous structural assignment. Density functional theory reproduces the experimentally observed structural features and identifies pronounced differences in intramolecular donor–acceptor interactions between the endo and exo hemispheres of the Pacman framework. Although donor–acceptor interactions are significantly weaker within the sterically confined Pacman cavity, the endo–exo isomers are predicted to be thermodynamically favored for both derivatives. The combined experimental and computational investigations provide a detailed understanding of the structural and electronic properties of these new phosphorus‐amino and phosphorus‐azido Pacman compounds and establish a basis for their future application as versatile precursors in main‐group chemistry.