Synthesis, Structure and Reactivities of Pentacoordinated Phosphorus–Boron Bonded Compounds,European Journal of Inorganic Chemistry

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Synthesis, Structure and Reactivities of Pentacoordinated Phosphorus–Boron Bonded Compounds
European Journal of Inorganic Chemistry ( IF 2.2 ) Pub Date : 2020-03-23 , DOI: 10.1002/ejic.202000229
Nathan J. O'Brien ₁ , Naokazu Kano ₁ , Nizam Havare ₁ , Ryohei Uematsu ₂ , Romain Ramozzi ₂ , Keiji Morokuma ₂

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The isolation and reactivities of two pentacoordinated phosphorus–tetracoordinated boron bonded compounds were explored. A highly Lewis acidic boron reagent and electron‐withdrawing ligand system were required to form the pentacoordinated phosphorus state of the P–B bond. The first compound, a phosphoranyl‐trihydroborate, gave a THF stabilised phosphoranyl‐borane intermediate upon a single hydride abstraction in THF. This compound could undergo a unique rearrangement, which involved a two‐fold ring expansion, to give a fused bicyclic compound or it could act as a mono‐hydroboration reagent. The hydroboration reactivity of the intermediate was found to be higher towards alkynes vs. alkenes, with good to moderate regioselectivity towards the terminal carbon. The second compound, a phosphoranyl‐triarylborate, was found to have different reactivity as it was highly stable towards acids and bases. This is thought to be due to the large bulk around the P–B bond as shown in the crystal structure.

中文翻译：

五配位磷-硼键合化合物的合成，结构和反应活性

研究了两种五配位磷-四配位硼键合化合物的分离和反应性。需要一种高度路易斯酸性的硼试剂和吸电子配体系统来形成PB键的五配位磷态。第一种化合物是三氢硼酸磷烷基酯，在THF中单氢化物萃取后就得到了THF稳定的磷烷基硼烷中间体。该化合物可能会发生独特的重排，涉及到两倍的环扩环，从而生成稠合的双环化合物，或者它可以用作单氢硼化试剂。发现中间体对炔烃的氢硼化反应性高于烯烃，对末端碳具有良好至中等的区域选择性。第二种化合物是磷酰基三芳基硼酸酯被发现具有不同的反应活性，因为它对酸和碱高度稳定。据认为，这是由于晶体结构中所示的PB键周围的大量堆积。

更新日期：2020-03-23

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