Using the Cambridge Structural Database, the frequencies of occurrence are determined for 6-fold phenyl embraces
(6PEs) between all fragments –XPh3, where X can be any tetrahedral atom. The relative frequencies are high for
the family of cations Ph4X+, highest of all for Ph4P+ where 1121 6PEs are found for 1647 cations. For R–XPh3
units (R≠Ph) with group IV and V central atoms, the relative frequencies are much lower, ranging between 13 and 28%
depending on R–X. It is very low, about 2%, for the Ph4B− anion and R–XPh3 groups with X=B, Al and Ga.
The formation of the hetero-pairs R1–XPh3···Ph3Y–R2
(X≠Y) is neither strongly favoured nor disfavoured over the formation of homo-pairs.
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