Department of Chemistry, University of Sussex, Falmer, Brighton, UK.
Dalton Trans. 2012 Jan 7;41(1):278-84. doi: 10.1039/c1dt11499a. Epub 2011 Nov 9.
The triphosphanes RMe(2)SiCH(2)P(PR'(2))(2) (R = Me, Ph; R' = SiMe(3), Cy) are synthesised in good yield via metathesis of organodichlorophosphanes and LiPR'(2), while for R' = Ph a propensity to form (Ph(2)P)(2) precludes isolation of the in situ characterised triphosphanes. Where R = Me and R' = SiMe(3) 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 (31)P{(1)H} NMR spectra manifesting anomalous 'second-order' characteristics, which are considered using full spin-Hamiltonian simulation. Preliminary studies of coordination chemistry and ancillary reactivity of the triphosphanes are described.
三膦烷 RMe(2)SiCH(2)P(PR'(2))(2) (R = Me, Ph; R' = SiMe(3), Cy) 可通过有机二氯膦烷和 LiPR'(2) 的复分解反应高产率合成，而对于 R' = Ph，存在形成 (Ph(2)P)(2) 的倾向，从而阻止了原位表征的三膦烷的分离。当 R = Me 且 R' = SiMe(3) 时，三膦烷也通过单晶 X 射线衍射进行了表征，在固态下表现出单一的几何构象，尽管溶液相 NMR 谱表明在很宽的温度范围内易于构象交换。所描述的所有三膦烷都表现出类似的行为，其各自的 (31)P{(1)H} NMR 谱表现出异常的“二阶”特征，这通过全自旋哈密顿模拟进行了考虑。还描述了三膦烷的配位化学和辅助反应性的初步研究。
