Aromaticity in P8 allotropes and (CH)8 analogues: significance of their 40 valence electrons?

The currently unknown phosphorus allotrope P8 is of interest since its 40 total valence electrons is a “magic number” corresponding to a filled 1S21P61D101S21F142P6 shell such as found in the relatively stable main group element clusters Al13− and Ge94−. However, P8 still remains as an elusive structure not realized experimentally. The lowest energy P8 structure by a margin of ∼9 kcal mol−1 is shown by density functional theory to be a cuneane analogue with no PP double bonds and two each of P5, P4, and P3 rings. Higher energy P8 structures are polycyclic systems having at most a single PP double bond. These P8 systems are not “carbon copies” of the corresponding (CH)8 hydrocarbons with exactly one hydrogen atom bonded to each carbon atom. Thus the lowest energy (CH)8 structure is cyclooctatetraene with four CC bonds followed by benzocyclobutene with three CC bonds. The cuneane (CH)8 structure is a relatively high energy isomer lying ∼36 kcal mol−1 above cyclooctatetraene. The cubane P8 and (CH)8 structures are even higher energy structures, lying ∼37 and ∼74 kcal mol−1 in energy above the corresponding global minima. Our results demonstrate differences in medium sized aggregates of elemental phosphorus and isolobal hydrocarbon species.