Formation of the elusive tetrahedral P3N molecule

Abstract

The tetrahedral 1,2,3-triphospha-4-azatricyclo [1.1.0.02,4] butane (P3N) molecule—an isovalent species of phosphorus (P4)—was prepared in low-temperature (5 K) phosphine-nitrogen ices and was identified in the gas phase through isomer-selective, tunable, soft photoionization reflectron time-of-flight mass spectrometry. Theoretical calculations reveal that the substitution of a single phosphorus atom by nitrogen in the P4 molecule results in enhanced spherical aromaticity while simultaneously increasing the strain energy from 74 to 195 kJ mol−1. In P3N, the P-P bond is shortened compared to those in P4 by 3.6 pm, while the P-N-P bond angle of 73.0° is larger by 13.0° compared to the P-P-P bond angle of 60.0° in P4. The identification of tetrahedral P3N enhances our fundamental understanding of the chemical bonding, electronic structure, and stability of binary, interpnictide tetrahedral molecules and reveals a universal route to prepare ring strained cage molecules in extreme environments.