Roy Matthew M D, Heilmann Andreas, Ellwanger Mathias A, Aldridge Simon
Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford, OX1 3QR, UK.
Angew Chem Int Ed Engl. 2021 Dec 13;60(51):26550-26554. doi: 10.1002/anie.202112515. Epub 2021 Nov 10.
By employing the highly reducing aluminyl complex [K{(NON)Al}] (NON=4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene), we demonstrate the controlled formation of P and P complexes from white phosphorus, and chemically reversible inter-conversion between them. The tetra-anion features a unique planar π-bonded structure, with the incorporation of the K cations implicit in the use of the anionic nucleophile offering additional stabilization of the unsaturated isomer of the P fragment. This complex is extremely reactive, acting as a source of P : exposure to ammonia leads to the release of phosphine (PH ) under mild conditions (room temperature and pressure), which contrast with those necessitated for the direct combination of P and NH (>5 kbar and >250 °C).
通过使用强还原性的铝基配合物[K{(NON)Al}]（NON = 4,5-双(2,6-二异丙基苯胺基)-2,7-二叔丁基-9,9-二甲基呫吨），我们展示了从白磷可控形成P 和P 配合物以及它们之间的化学可逆相互转化。该四阴离子具有独特的平面π键合结构，使用阴离子亲核试剂时隐含的K阳离子的引入为P 片段的不饱和异构体提供了额外的稳定性。这种配合物极具反应性，可作为P 的来源：在温和条件（室温及常压）下，与氨接触会导致磷化氢（PH ）的释放，这与P和NH直接化合所需的条件（>5 kbar和>250 °C）形成对比。
