作者:Charlotte E. Averre、Martyn P. Coles、Ian R. Crossley、Iain J. Day
DOI:10.1039/c1dt11499a
日期:——
The triphosphanes RMe2SiCH2P(PRâ²2)2 (R = Me, Ph; Râ² = SiMe3, Cy) are synthesised in good yield viametathesis of organodichlorophosphanes and LiPRâ²2, while for Râ² = Ph a propensity to form (Ph2P)2 precludes isolation of the in situ characterised triphosphanes. Where R = Me and Râ² = SiMe3 the triphosphane has also been characterised by single crystal X-ray diffraction and exhibits a single geometric conformer in the solid state, though solution-phase NMR spectra are indicative of facile conformational exchange across a wide temperature range. All of the described triphosphanes exhibit comparable behaviour, with their respective 31P1H} NMR spectra manifesting anomalous âsecond-orderâ characteristics, which are considered using full spin-Hamiltonian simulation. Preliminary studies of coordination chemistry and ancillary reactivity of the triphosphanes are described.
RMe2SiCH2P(PRâ²2)2(R=Me,Ph;Râ²=SiMe3,Cy)是由有机二氯膦和 LiPRâ²2 二甲氧基化合成的,产量很高,而 Râ²=Ph 时,形成 (Ph2P)2 的倾向排除了原位分离三膦的可能性。在 R = Me 和 Râ² = SiMe3 的情况下,三膦烷也通过单晶 X 射线衍射进行了表征,并在固态下显示出单一的几何构象,但溶液相核磁共振光谱表明,在很宽的温度范围内,构象易发生交换。所有描述的三膦化合物都表现出相似的行为,它们各自的 31P1H} NMR 光谱都表现出反常的变化。NMR 光谱显示出反常的 "二阶 "特征,我们利用全自旋-哈密顿模拟对其进行了研究。报告还介绍了对三膦酸配位化学和辅助反应性的初步研究。