<i>Peri</i>-Substituted Phosphorus–Tellurium Systems–An Experimental and Theoretical Investigation of the P···Te through-Space Interaction

A series of peri-substituted phosphorus–tellurium systems R′Te–Acenap–PR2 (R′ = Ph, p-An, Nap, Mes, Tip; Acenap = acenaphthene-5,6-diyl (–C12H8); R = iPr, Ph) exhibiting large “through-space” spin–spin coupling constants and the “onset” of three-center four-electron type interactions is presented. The influence of the substituents at the phosphorus and tellurium atoms as well as their behavior upon oxidation (with S, Se) or metal-coordination (Pt, Au) is discussed using NMR spectroscopy, single-crystal X-ray diffraction, and advanced density functional theory studies including NBO, AIM, and ELI-D analyses.