Theoretical and X‐Ray Evidence of Electrostatic Phosphonium anti and gauche Effects

Sulphur, not phosphorus, is the only known third‐row element capable of experiencing an electrostatic gauche effect with fluorine. Some six‐membered rings containing an endocyclic phosphorus atom and a β‐fluorine substituent that can interconvert to axial (gauche relative to phosphorus) and equatorial positions were then analysed. While phosphines do not establish an electrostatic attraction between fluorine and phosphorus, some oxidised forms exhibit surprising stability for the sterically disfavoured axial orientation. Because the nature of this behaviour was not obvious, since an intramolecular hydrogen bond can appear, a phosphonium derivative was further studied and its axial conformation was found to be highly stable. A preference for the gauche arrangement appears even for the acyclic and sterically hindered (2‐fluoroethyl)triphenylphosphonium cation. On the other hand, (ethane‐1,2‐diyl)bis(phosphonium) cations are exclusively in anti conformation due to an (+/+)‐electrostatic repulsion between the positively charged phosphonium groups. Electrostatic! An electrostatic attraction between organic fluorine and phosphorus does not appear in phosphines and phosphine oxides, but it strongly stabilises the gauche conformation in β‐fluoro‐ethylphosphonium cations, both in solution and solid state. On the other hand, (+/+)‐electrostatic repulsion, not steric effects, in bis‐phosphonium cations leads to an anti geometry.