Novel spirophosphoranes (O-cis) that exhibit reversed apicophilicity having an apical carbon-equatorial oxygen array in a five-membered ring showed enhanced reactivity toward nucleophiles such as n-Bu(4)N(+)F(-) or MeLi in comparison with the corresponding stable isomeric spirophosphoranes (O-trans) having an apical oxygen-equatorial carbon configuration. The enhanced reactivity of the O-cis isomer could be explained by the presence of a lower-lying sigma(P)(-)(O(equatorial)) orbital as the reacting orbital in the equatorial plane, whereas the corresponding orbital is a higher-lying sigma(P)(-)(C(equatorial)) in the O-trans isomer. Density functional theory (DFT) calculation on the actual compounds provided theoretical support for this assumption. In addition, we found that the benzylic anion alpha to the phosphorus atom in O-cis benzyl phosphorane is much more stable than that generated from the corresponding O-trans compounds. The experimental results were considered to be due to the n(C) --> sigma(P)(-)(O) interaction in the O-cis anion, and this was confirmed by DFT calculations. Furthermore, the hexacoordinate anionic species derived from the reaction of the benzylic anion from O-cis benzylphosphorane with an aldehyde was also found to be stabilized as compared with analogous species from the corresponding O-trans isomer. The first X-ray structural characterization of a hexacoordinate phosphate intermediate in the Wittig type reaction using pentacoordinate phosphoranes is reported.