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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Photoactivated silicon-oxygen and silicon-nitrogen heterodehydrocoupling with a commercially available iron compound
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Photoactivated silicon-oxygen and silicon-nitrogen heterodehydrocoupling with a commercially available iron compound

机译：具有市售铁化合物的光活化的硅氧和硅氮杂耦合

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摘要

Silicon-oxygen and silicon-nitrogen heterodehydrocoupling catalyzed by the commercially available cyclopentadienyl dicarbonyl iron dimer [CpFe(CO)(2)](2) (1) under photochemical conditions is reported. Reactions between alcohols and PhSiH3 with catalytic 1 under visible-light irradiation produced silyl ethers quantitively. Reactions between either secondary or tertiary silanes and alcohols also produced silyl ethers, however, these reactions were marked by their longer reaction times and lower conversions. Reactions of either primary or secondary amines and silanes with catalytic 1 demonstrated mixed efficiency, featuring conversions of 20-100%. Mechanistic study indicates that an iron silyl compound is unimportant in the bond-formation step and argues for either a nucleophilic alkoxide or amide intermediate. Most important, mechanistic study reveals that the most immediate hurdle in the catalysis is the poor activation of 1, demonstrating the necessity to fully activate the catalyst to realize the potential of iron in this reactivity.
机译：据报道，通过市售环戊二烯基二羰基二聚体[CPFE（CO）（2）（2）（2）（2）在光化学条件下催化的硅 - 氧和硅氮杂耦合。在可见光照射下醇和Phsih3与催化1之间的反应定量地产生了甲硅烷基醚。二级或叔硅烷和醇之间的反应也产生了甲硅烷基醚，然而，这些反应的较长反应时间和较低的转化率标记。用催化1的伯胺或仲胺和硅烷的反应表现出混合效率，具有20-100％的转化。机械研究表明铁甲硅烷基化合物在粘合形成步骤中不重要，并争论亲核醇盐或酰胺中间体。最重要的，机械研究表明，催化中最直接的障碍是1的差，表明必须完全激活催化剂以实现这种反应性的潜力。

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