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.
J Chem Theory Comput. 2008 Jan;4(1):49-63. doi: 10.1021/ct700220z.
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.
五配位磷与四配位磷化合物的亲核取代反应有关，在其几何和能量特征方面表现出很大的可变性。通过对一系列基本模型化合物的系统理论研究，我们分析了键合特征。五配位磷化合物通过配位键结合在一起，其几何形状和稳定性取决于磷上不同取代基引起的诱导效应。我们还表明，外电场可以改变亲核取代反应的几何特征和反应性。在涉及五配位磷的生物反应中，这个问题可能非常重要，因为折叠蛋白质产生的电场可能会影响催化过程。我们还报告了对三种三苯基膦叶立德衍生物的几何形状和 NMR 谱的附加计算，我们的结果与实验数据很好地吻合。
