Phosphaketenes as Building Blocks for the Synthesis of Triphospha Heterocycles
Phosphaketenes as Building Blocks for the Synthesis of Triphospha Heterocycles
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DOI：
10.1002/chem.201403419
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发表时间：
2014-09-01
影响因子：
4.3
通讯作者：
Gruetzmacher, Hansjoerg
中科院分区：
文献类型：
--
作者：
Heift, Dominikus;Benko, Zoltan;Gruetzmacher, Hansjoerg
不饱和磷化合物，如磷杂烯烃和磷杂炔，在环加成反应中表现出多种反应活性。尽管磷烯酮（R-P=C=O）已经被人们认识了三十年，但它们的化学性质仍然有限。本文中，我们表明，杂原子取代的磷烯酮，R3 E-P =C=O（E=Si，Sn），是硅烷基和甲锡烷基取代的五元杂环含有三个磷原子的积木。杂环阴离子的结构取决于所涉及的四元原子的性质。虽然甲硅烷基类似物[P3 C2（OSiR 3）（2）]（-）是一种芳香族1，2，4-三磷脂，但甲锡烷基化合物[P（CO）（2）（PSnR 3）（2）]（-）是一种具有离域OCPCO片段的1，2，4-三磷酸环戊-3，5-二酮。由于它们的阴离子特性，这些化合物可以容易地用作结构单元，例如，在甲硅烷基官能化的六磷杂二茂铁或母体1，2，4-三磷杂环戊-3，5-二酮[P（CO）（2）（PH）（2）]（-）的制备中。NMR光谱研究和计算表明，本文提出的杂环形成反应非常复杂。
Unsaturated phosphorus compounds, such as phosphaalkenes and phosphaalkynes, show a versatile reactivity in cycloadditions. Although phosphaketenes (R-P=C=O) have been known for three decades, their chemistry has remained limited. Herein, we show that heteroatom-substituted phosphaketenes, R3E-P=C=O (E=Si, Sn), are building blocks for silyl- and stannyl-substituted five-membered heterocycles containing three phosphorous atoms. The structure of the heterocyclic anion depends on the nature of the tetrel atom involved. Although the silyl analogue [P3C2(OSiR3)(2)](-) is an aromatic 1,2,4-triphospholide, the stannyl compound [P(CO)(2)(PSnR3)(2)](-) is a 1,2,4-triphosphacyclopenta-3,5-dionate with a delocalized OCPCO fragment. Because of their anionic character, these compounds can easily be used as building blocks, for example, in the preparation of a silyl-functionalized hexaphosphaferrocene or the parent 1,2,4-triphosphacyclopenta-3,5-dionate [P(CO)(2)(PH)(2)](-). NMR spectroscopic investigations and computations have shown that the heterocycle-formation reactions presented herein are remarkably complex.