Theoretical Interpretation of 31P NMR Chemical Shifts. III. Phosphorus with Five Like Substituents

Abstract
Using the assumption that the valence orbital hybridization in compounds of the type PZ5 is such that all five fluorines in PF5 are instantaneously magnetically equivalent even though the two axial bond lengths are longer than the three equatorial ones in this trigonal bipyramidal structure, an ASP LCAO MO quantum‐mechanical calculation has been made for the 31P chemical shifts of molecules of the form PZ5. As in the two previous papers of this series, π bonding to the phosphorus is included. On the assumption that the π orbitals of the phosphorus are vacant in the compound P (C6H5)5, the amount of π bonding is estimated for the symmetrically substituted compounds of the type PZ5 on which chemical‐shift data are available.

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