the magnitudinal differences in reactions rates allowed for a proposed reaction scheme wherein, a pre-rate determining attack of the tetravalent silane by the nucleophile results in an equilibrium between the neutral tetracoordinated species and the anionic pentavalent compound. This is followed by nucleophilic coordination by two Grignard reagents as normally seen, forming a hexacoordinated transition state and yielding the expected product. The mechanistic implications of this are extended to a hexacoordinated silicon species that is thought to be active as a transition state in some reactions. The reaction of allyl- or crotyl-trifluorosilanes with aldehydes and ketones only precedes with fluoride activation to give a pentacoordinated silicon. This intermediate then acts as a Lewis acid to coordinate with the carbonyl oxygen atom. The further weakening of the silicon–carbon bond as the silicon becomes hexacoordinate helps drive this reaction. Phosphorus Similar reactivity has also been observed for other hypervalent structures such as the miscellany of phosphorus compounds, for which hexacoordinated transition states have been proposed. Hydrolysis of phosphoranes and oxyphosphoranes have been studied and shown to be second order in water. Bel'skii et al.. have proposed a prerate determining nucleophilic attack by water resulting in an equilibrium between the penta- and hexacoordinated phosphorus species, which is followed by a proton transfer involving the second water molecule in a rate determining ring-opening step, leading to the hydroxylated product. Alcoholysis of pentacoordinated phosphorus compounds, such as trimethoxyphospholene with benzyl alcohol, have also been postulated to occur through a similar octahedral transition state, as in hydrolysis, however without ring opening. It can be understood from these experiments that the increased reactivity observed for hypervalent molecules, contrasted with analogous nonhypervalent compounds, can be attributed to the congruence of these species to the hypercoordinated activated states normally formed during the course of the reaction. Ab initio calculations The enhanced reactivity at pentacoordinated silicon is not fully understood. Corriu and coworkers suggested that greater electropositive character at the pentavalent silicon atom may be responsible for its increased reactivity. Preliminary ab initio calculations supported this hypothesis to some degree, but used a small basis set. A software program for ab initio calculations, Gaussian 86, was used by Dieters and coworkers to compare tetracoordinated silicon and phosphorus to their pentacoordinate analogues. This ab initio approach is used as a supplement to determine why reactivity improves in nucleophilic reactions with pentacoordinated compounds. For silicon, the 6-31+G* basis set was used because