Structure of diiodine adducts of some di- and tri-tertiaryphosphines in the solid state and in solution
Structure of diiodine adducts of some di- and tri-tertiaryphosphines in the solid state and in solution
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DOI：
10.1039/a706277j
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发表时间：
1998
期刊：
影响因子：
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通讯作者：
N. Bricklebank;S. Godfrey;C. McAuliffe;P. Deplano;M. L. Mercuri;J. M. Sheffield
中科院分区：
文献类型：
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作者：
N. Bricklebank;S. Godfrey;C. McAuliffe;P. Deplano;M. L. Mercuri;J. M. Sheffield
合成了一系列二叔膦-四碘加合物R_2P（I_2）（CH_2）_3（I_2）R_2（R = Ph，n = 1-4; R = PhCH_2或o-CH_3C_6 H_4，n = 2）和两种三叔膦-六碘加合物PhP（CH_2CH_2 PPh_2）_2I_6和CH_3C（CH_2 PPh_2）_3I_6，并用~（31）P-{H}溶液NMR和拉曼光谱进行了表征。在Ph_2P（I_2）（CH_2）_（I_2）Ph_2（n = 2或4）的情况下，已使用~（31）P-{H} NMR魔角旋转NMR光谱来研究固态化合物的性质。与我们以前对单膦衍生物R3 PI 2的广泛研究一致，从乙醚中分离的四碘双膦化合物Ph 2 P（I2）（CH 2）n（I2）Ph 2（n = 2或4）含有分子四配位磷中心，二碘以线性辐条的形式结合在其上，如在CDCl 3溶液中获得的它们的31 P-{H} NMR位移所示。同样，与我们先前对单膦衍生物R3 PI 2的溶液研究一致，二膦-四碘加合物在CDCl 3溶液中完全电离，产生离子化合物[R2 P（I）（CH 2）R2（I）R2] 2 I;溶液31 P-{H} NMR位移与先前归属于[R3 PI]I的类似溶液位移非常相似。在化合物中发现了与ν（P-I）有关的拉曼谱带，并观察到与ν（I-I）有关的另一个低频谱带。虽然没有记录到三膦-六碘加合物的固态NMR谱，但在拉曼谱中观察到可归属于ν（I-I）的带，表明这些六碘三叔膦化合物在固态下也普遍存在分子四配位辐条结构。从溶液31 P-{H} NMR位移，这些加合物也似乎在CDCl 3溶液中电离。
A series of ditertiaryphosphine–tetraiodine adducts R2P(I2)(CH2)nP(I2)R2 (R = Ph, n = 1–4; R = PhCH2 or o-CH3C6H4, n = 2) and two tritertiaryphosphine–hexaiodine adducts, PhP(CH2CH2PPh2)2I6 and CH3C(CH2PPh2)3I6 have been prepared and characterised by 31P-{H} solution NMR and Raman spectroscopy. In the case of Ph2P(I2)(CH2)nP(I2)Ph2 (n = 2 or 4), 31P-{H} NMR magic angle spinning NMR spectroscopy has been used to investigate the nature of the compounds in the solid state. In agreement with our previous extensive studies on the monophosphine derivatives, R3PI2, the tetraiododiphosphine compounds Ph2P(I2)(CH2)nP(I2)Ph2 (n = 2 or 4) isolated from diethyl ether contain molecular four-co-ordinate phosphorus centres onto which the diiodine is bound as a linear spoke, as indicated by their 31P-{H} NMR shifts obtained in CDCl3 solution. Again, in agreement with our previous solution studies of the monophosphine derivatives R3PI2, the diphosphine–tetraiodine adducts completely ionise in CDCl3 solution to produce the ionic compounds [R2P(I)(CH2)nP(I)R2]2I; the solution 31P-{H} NMR shifts are very similar to analogous solution shifts previously assigned to [R3PI]I. The Raman band assignable to ν(P–I) has been identified for the compounds and a further band at lower frequency has been observed and assigned to ν(I–I). Although the solid-state NMR spectra of the triphosphine–hexaiodine adducts were not recorded, a band assignable to ν(I–I) was observed in the Raman spectrum, suggesting the molecular four-co-ordinate spoke structure also prevails for these hexaiodotritertiaryphosphine compounds in the solid state. From solution 31P-{H} NMR shifts these adducts also appear to ionise in CDCl3 solution.