title: Inductive and External Electric Field Effects in Pentacoordinated Phosphorus Compounds.
abstract: Pentacoordination at phosphorus is associated with a nucleophilic displacement reaction at tetracoordinated phosphorus compounds and shows a great variability in what respects their geometrical and energetic features. By means of a systematic theoretical study on a series of elementary model compounds, we have analyzed the bonding features. The pentacoordinated phosphorus compounds are held together by dative bonds, and the geometry and stability depends on the inductive effects originated by different substitutes at phosphorus. We show also that an external electric field can modify the geometrical features and the reactivity of the nucleophilic substitution reactions. This issue may have great interest in biological reactions involving pentacoordinated phosphorus where the electric field originated by the folded protein could influence the catalytic process. We report also additional calculations on the geometry and NMR spectra on three triphenyl phosphonium ylide derivatives, and our results compare well with the experimental data.
authors.affiliation: Grup de Química Teòrica i Computacional, Departament de Química Orgànica Biològica, Institut d'Investigacions Químiques i Ambientals de Barcelona, IIQAB - CSIC, c/ Jordi Girona 18, E-08034 Barcelona, Spain.
authors.forename: Enrique
authors.initials: E
authors.lastname: Marcos
authors.affiliation: Grup de Química Teòrica i Computacional, Departament de Química Orgànica Biològica, Institut d'Investigacions Químiques i Ambientals de Barcelona, IIQAB - CSIC, c/ Jordi Girona 18, E-08034 Barcelona, Spain.
authors.forename: Ramon
authors.initials: R
authors.lastname: Crehuet
authors.affiliation: Grup de Química Teòrica i Computacional, Departament de Química Orgànica Biològica, Institut d'Investigacions Químiques i Ambientals de Barcelona, IIQAB - CSIC, c/ Jordi Girona 18, E-08034 Barcelona, Spain.
authors.forename: Josep M
authors.initials: JM
authors.lastname: Anglada