New Anions of Pentacoordinate Phosphorus Containing Fluorine and Trifluoromethyl Groups
作者:Natalya V. Pavlenko、Lesya A. Babadzhanova、Igor I. Gerus、Yurii L. Yagupolskii、Wieland Tyrra、Dieter Naumann
DOI:10.1002/ejic.200600974
日期:2007.4
(PhO)3P(O), Me3SiCF3 and the fluoride ion sources [Me4N]F and CsF, respectively, in glyme. These anions represent the stable transition states postulated for nucleophilic substitution at a tetrahedral phosphorus atom. The salt Cs[(CF3)2PF2O] (7) is stable at room temperature for a month, while [Me4N][CF3PF3O] (1) dismutates into [Me4N][CF3PF(O)O] (2) and [Me4N][CF3PF5] (3) above 0 °C. (© Wiley-VCH Verlag
首次获得并表征了独特的伪三角双锥体 CF3PF3O– 和 (CF3)2PF2O– 阴离子。它们分别由 (PhO)3P(O)、Me3SiCF3 和氟离子源 [Me4N]F 和 CsF 在甘醇二甲醚中反应形成。这些阴离子代表在四面体磷原子处亲核取代所假定的稳定过渡态。盐 Cs[(CF3)2PF2O] (7) 在室温下稳定一个月,而 [Me4N][CF3PF3O] (1) 歧化为 [Me4N][CF3PF(O)O] (2) 和 [Me4N] [CF3PF5] (3) 高于 0 °C。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)