title: Pentacoordinate oxyphosphorane intermediate always exists in aqueous solution.
abstract: Gas-phase ab initio calculations indicate that dianionic pentacoordinate oxyphosphoranes do not have a kinetically meaningful intermediate. The simplest oxyphosphorane PO5H3(2-) has the least tendency to have a pentacoordinate intermediate. However, it does have a pentacoordinate intermediate when it is solvated with six water molecules. These results support the hypothesis that the phosphoryl transfer reactions take place via pentacoordinate intermediate not only in acidic but also in basic media.
authors.affiliation: Technical Research Centre, Chemical Laboratory, Finland.
authors.forename: A
authors.initials: A
authors.lastname: Yliniemela
authors.forename: T
authors.initials: T
authors.lastname: Uchimaru
authors.forename: K
authors.initials: K
authors.lastname: Tanabe
authors.forename: M
authors.initials: M
authors.lastname: Uebayasi
authors.forename: K
authors.initials: K
authors.lastname: Taira
mesh_terms: D007700:Kinetics; D010753:Phosphoranes / Q000737:chemistry*; D012996:Solutions; D014867:Water / Q000737:chemistry
chemical_list: D010753:Phosphoranes; D012996:Solutions; D014867:Water