Abstract
Abstract Pseudorotation of a trigonal-bipyramidal intermediate has been postulated recently by a number of investigators2-5 concerned with various aspects of phosphorus chemistry. We wish to report results defining the requirements for such a process for phosphorus pentahalide molecules (known to undergo intramolecular exchange) and provide useful criteria in analyzing possible related situations. What is being considered here is a process analogous in some respects to the inversion occurring in the ammonia molecule.6 In the case of trigonal-bipyramidal molecules an internal vibration is thought to lead to exchange of equatorial and axial positions, leaving the molecule rotated compared to its original state (Figure 1). This type of process was first postulated by Berry7 to rationalize the appearance of equivalent fluorine environments in the 19F nmr spectrum8 of trigonal-bipyramidal PF5 Nmr studies have now revealed examples of several trigonal-bipyramidal phosphorus compounds, PCl2F3,9,10 PH2F3 11 (CH2H...
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