Abstract: Two very stable PH phosphoranes, 13 and 19, each containing two aryl and two alkoxy ligands, are prepared by LiAIH4 reduction of spirobicyclic phosphonium salt 12 or reaction of PC13 with the Grignard reagent made from bromo alcohol 18, respectively. Evidence is presented for the intermediate formation of tetracoordinate trigonal bipyramidal phosphoranide anions, conjugate bases of the PH phosphoranes, in these syntheses. The ...