Reactivity of phosphiranes toward nucleophiles: Theoretical and experimental investigations
作者:Michelle L. Coote、Elizabeth H. Krenske、Ilham Maulana、Jörg Steinbach、S. Bruce Wild
DOI:10.1002/hc.20405
日期:2008.3
The thermodynamic and kinetic parameters for the reaction of 1-methylphosphirane with dimethylphosphide (PMe), proceeding via attack at the ring phosphorus atom to give Me2P–PMe− plus ethylene, were calculated at the G3(MP2)-RAD(+) level. The rate constant for this mechanism (k = 1.1 × 1013 L mol−1 s−1 at 25°C) is seven orders of magnitude greater than that for the previously studied mechanism involving
1-甲基膦与二甲基磷化物(PMe)反应的热力学和动力学参数,通过攻击环磷原子得到Me2P-PMe-加乙烯,在G3(MP2)-RAD(+)水平计算。这种机制的速率常数(k = 1.1 × 1013 L mol-1 s-1 在 25°C 下)比先前研究的涉及碳侵蚀的机制的速率常数大七个数量级。用 1-苯基膦进行的实验研究给出了一致的结果:用 LiPMePh 处理没有产生可检测的聚合物,用 MeI 淬灭得到已知的二膦 (R*, R*)-(±)/(R*, S*)-MePhP--PMePh . © 2008 Wiley Periodicals, Inc. 杂原子化学 19:178–181, 2008; 在线发表于 Wiley InterScience (www.interscience.wiley.com)。DOI 10.1002/hc.20405