Synthesis and ligand properties of silsesquioxane‐caged phosphite T7Ph7P

Marc Hunsicker, Johannes Krebs, Michael Zimmer, Bernd Morgenstern, Volker Huch, D. Scheschkewitz
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Abstract

The synthesis of the phosphorus‐capped heptaphenylsilsesquioxane T7Ph7P is reported. We show that, unlike previous examples, it readily forms Lewis acid‐base adducts with boranes of different steric demand and the FeCO4 fragment. All complexes were characterized by multinuclear NMR and IR spectroscopy in solution and the solid state. The molecular structures of the adducts with BPh3 and B(C6F5)3 were determined from XRD suitable single crystals. The relative conformation of the Ph and C6F5 rings in T7Ph7P‐B(C6F5)3 suggests favorable π‐interactions, stabilizing the adducts to such a degree that attempts to activate H2 or CO2 were unsuccessful.
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硅倍半氧烷笼型亚磷酸酯 T7Ph7P 的合成和配体特性
报告了磷封端的七苯基硅倍半氧烷 T7Ph7P 的合成过程。我们发现,与以前的例子不同,它很容易与不同立体需求的硼烷和 FeCO4 片段形成路易斯酸碱加合物。我们通过多核核磁共振和红外光谱对溶液和固体状态下的所有配合物进行了表征。与 BPh3 和 B(C6F5)3 的加合物的分子结构是通过适合单晶体的 XRD 确定的。T7Ph7P-B(C6F5)3 中 Ph 环和 C6F5 环的相对构象表明了有利的 π 相互作用,从而稳定了加合物,以至于激活 H2 或 CO2 的尝试都没有成功。
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