First X-ray crystal study and DFT calculations of anionic λ4-phosphinines
First X-ray crystal study and DFT calculations of anionic λ4-phosphinines
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DOI：
10.1021/om030023x
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发表时间：
2003-04-28
期刊：
影响因子：
2.8
通讯作者：
Mézailles, N
中科院分区：
文献类型：
--
作者：
Moores, A;Ricard, L;Mézailles, N
通过相应的λ（3）-膦1和2与MeLi的反应合成阴离子λ（4）-膦3和4。报道了[3][Li（thf）（2）]的X-射线结构，并表明Li阳离子与磷杂环己二烯基部分的5个碳原子的eta（5）-配位。还合成了穴状物种[3] [Li [2.2.2]]和[41][Li（thf）（4）]，并通过X射线衍射方法进行了分析，从而可以与非穴状物种进行直接比较。阴离子5由2与t-BuLi反应得到。这表明，电子和立体可以很容易地修改这些高活性物种。给出了[51 [Li [2.2.2]]的晶体结构。这项研究是通过DFT计算完成的，它表明负电荷基本上定位在这些阴离子的a碳原子上。
Anionic lambda(4)-phosphinines 3 and 4 were synthesized via the reaction of the corresponding lambda(3)-phosphinines 1 and 2 with MeLi. The X-ray structure of [3][Li(thf)(2)] is reported and shows the eta(5)-coordination of the Li cation to the five carbon atoms of the phosphacyclohexadienyl moiety. Cryptated species [3] [Li [2.2.2]] and [41[Li(thf)(4)]were also synthesized and analyzed by X-ray diffraction methods, allowing direct comparison with noncryptated species. Anion 5 was obtained by the reaction of 2 with t-BuLi. This shows that electronics and sterics can easily be modified on these highly reactive species. The crystal structure of [51 [Li [2.2.2]] is presented. This study was completed by DFT calculations, which showed the negative charge to be essentially localized on the a carbon atoms of these anions.