期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 20, 期 36, 页码 11326-11330出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201403419
关键词
NMR spectroscopy; phosphaketenes; phosphorus heterocycles; reaction mechanisms; sandwich complexes
资金
- Swiss National Science Foundation (SNF)
- ETH Zurich
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.
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