Sterically Crowded peri-Substituted Naphthalene Phosphines and their PV Derivatives
Sterically Crowded peri-Substituted Naphthalene Phosphines and their PV Derivatives
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DOI：
10.1002/chem.201000454
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发表时间：
2010-01-01
影响因子：
4.3
通讯作者：
Woollins, J. Derek
中科院分区：
文献类型：
--
作者：
Knight, Fergus R.;Fuller, Amy L.;Woollins, J. Derek
合成了三个空间拥挤的含硫和磷的萘膦衍生物Nap[PPh 2][ER]（Nap =萘-1，8-二基; ER = SEt，SPh，SePh）1-3.每个膦反应形成完整系列的P-Y硫属化物Nap[P（E '）-（Ph-2）（ER）]（E' = 0、S、Se）。通过X射线晶体学、多核NMR谱、IR谱和MS对新化合物进行了表征。比较了1，2，nO，nS，nSe（n = 1-3）的X射线数据。用萘环扭转、笔原子位移、张开角大小、X中心点中心点中心点E相互作用、芳环取向和准线性排列分析了11种分子结构。随着重硫族元素原子的引入，萘区域的拥挤程度增加，同时萘的畸变也普遍增加。PE的距离增加的分子，包含体积较大的原子的位置，也当较大的硫族元素原子被绑定到磷。硫族化物采用类似的构象，其包含准线性E中心点P-C片段，除了30，其显示扭曲-轴向-扭曲构象，导致形成线性O中心点Se-C配向。对20，30，3S和3Se进行的从头计算显示Wiberg键指数值为0.02至0.04，这表明只有很小的非键相互作用;然而，对30，3S和3Se的自由基阳离子的计算显示增加的值（0.14-0.19）。
Three sterically crowded pen-substituted naphthalene phosphines, Nap[PPh2][ER] (Nap = naphthalene-1,8-diyl; ER = SEt, SPh, SePh) 1-3, which contain phosphorus and chalcogen functional groups at the peri positions have been prepared. Each phosphine reacts to form a complete series of P-Y chalcogenides Nap[P(E')-(Ph-2)(ER)] (E' = O, S, Se). The novel compounds were fully characterised by using X-ray crystallography and multinuclear NMR spectroscopy, IR spectroscopy and MS. X-ray data for 1, 2, nO, nS, nSe (n = 1-3) are compared. Eleven molecular structures have been analysed by naphthalene ring torsions, pen-atom displacement, splay angle magnitude, X center dot center dot center dot E interactions, aromatic ring orientations and quasi-linear arrangements. An increase in the congestion of the peri region following the introduction of heavy chalcogen atoms is accompanied by a general increase in naphthalene distortion. PE distances increase for molecules that contain bulkier atoms at the peri positions and also when larger chalcogen atoms are bound to phosphorus. The chalcogenides adopt similar conformations that contain a quasi-linear E center dot center dot center dot P-C fragment, except for 30, which displays a twist-axial-twist conformation resulting in the formation of a linear O center dot center dot center dot Se-C alignment. Ab initio MO calculations performed on 20, 30, 3S and 3Se reveal Wiberg bond index values of 0.02 to 0.04, which indicates only minor non-bonded interactions; however, calculations on radical cations of 30, 3S and 3Se reveal increased values (0.14-0.19).