Volodarsky Solomon, Malahov Irina, Bawari Deependra, Diab Mohand, Malik Naveen, Tumanskii Boris, Dobrovetsky Roman
School of Chemistry, Raymond and Beverly Sackler Faculty of Exact Sciences, Tel Aviv University Department Tel Aviv 69978 Israel
Department of Molecular Chemistry and Materials Science, Weizmann Institute of Science Rehovot 7610001 Israel.
Chem Sci. 2022 Apr 27;13(20):5957-5963. doi: 10.1039/d2sc01060g. eCollection 2022 May 25.
Geometrical constriction of main group elements leading to a change in the reactivity of these main group centers has recently become an important tool in main group chemistry. A lot of focus on using this modern method is dedicated to group 15 elements and especially to phosphorus. In this work, we present the synthesis, isolation and preliminary reactivity study of the geometrically constrained, square pyramidal (SP) phosphoranide anion (1). Unlike, trigonal bipyramidal (TBP) phosphoranides that were shown to react as nucleophiles while their redox chemistry was not reported, 1 reacts both as a nucleophile and reductant. The chemical oxidation of 1 leads to a P-P dimer (1-1) that is formed the dimerization of unstable SP phosphoranyl radical (1˙), an unprecedented decay pathway for phosphoranyl radicals. Reaction of 1 with benzophenone leads a single electron transfer (SET) to 1-OK and corresponding tetraphenyl epoxide (4).
主族元素的几何限制导致这些主族中心反应性的变化，最近已成为主族化学中的一种重要工具。许多对这种现代方法的关注都集中在第15族元素，尤其是磷上。在这项工作中，我们展示了几何受限的正方锥（SP）磷化物阴离子（1）的合成、分离及初步反应性研究。与已显示作为亲核试剂反应但未报道其氧化还原化学的三角双锥（TBP）磷化物不同，1既作为亲核试剂又作为还原剂反应。1的化学氧化导致形成一个P-P二聚体（1-1），它由不稳定的SP磷酰基自由基（1˙）二聚而成，这是磷酰基自由基前所未有的衰变途径。1与二苯甲酮反应导致单电子转移（SET）生成1-OK和相应的四苯基环氧化物（4）。
