Phosphaketenes as Building Blocks for the Synthesis of Triphospha Heterocycles |
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| Authors: | Dr. Dominikus Heift Dr. Zoltán Benkő Prof. Dr. Hansjörg Grützmacher |
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| Affiliation: | 1. Department of Chemistry and Applied Biosciences, ETH Zurich, CH‐8093 Zurich (Switzerland);2. Lehn Institute of Functional materials (LIFM), Sun Yat‐Sen University, 510275 Guangzhou (P.R. China) |
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| Abstract: | 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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| Keywords: | NMR spectroscopy phosphaketenes phosphorus heterocycles reaction mechanisms sandwich complexes |
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