Stereoelectronic Effects on the One-Electron Donor Reactivity of Trivalent Phosphorus Compounds. Experimental and Theoretical Investigations

Article abstract of DOI:10.1246/bcsj.71.927

Peak oxidation potentials E_p^ox of acyclic and cyclic phosphinites, phosphonites, and phosphites were measured by cyclic voltammetry. The inductive effect of the ligands attached to the phosphorus is a primary factor to determine _p^ox of these compounds. The geometry of the compound is another important factor; _p^ox is lowered when the compound adopts a geometry in which the phosphorus lone-pair orbital overlaps with the adjacent oxygen p-orbital. The stereoelectronic effects found here are interpreted in terms of the energy level of the highest occupied molecular orbital (HOMO) of these phosphorus compounds.