Hoidn Christian M, Scott Daniel J, Wolf Robert
University of Regensburg, Institute of Inorganic Chemistry, 93040, Regensburg, Germany.
Chemistry. 2021 Jan 26;27(6):1886-1902. doi: 10.1002/chem.202001854. Epub 2020 Nov 18.
Recently there has been great interest in the reactivity of transition-metal (TM) centers towards white phosphorus (P ). This has ultimately been motivated by a desire to find TM-mediated alternatives to the current industrial routes used to transform P into myriad useful P-containing products, which are typically indirect, wasteful, and highly hazardous. Such a TM-mediated process can be divided into two steps: activation of P to generate a polyphosphorus complex TM-P , and subsequent functionalization of this complex to release the desired phosphorus-containing product. The former step has by now become well established, allowing the isolation of many different TM-P products. In contrast, productive functionalization of these complexes has proven extremely challenging and has been achieved only in a relative handful of cases. In this review we provide a comprehensive summary of successful TM-P functionalization reactions, where TM-P must be accessible by reaction of a TM precursor with P . We hope that this will provide a useful resource for continuing efforts that are working towards this highly challenging goal of modern synthetic chemistry.
最近，人们对过渡金属（TM）中心与白磷（P₄）的反应性产生了浓厚兴趣。这最终源于一种愿望，即寻找由TM介导的替代当前工业路线的方法，当前工业路线用于将P₄转化为无数有用的含磷产品，这些路线通常间接、浪费且高度危险。这种由TM介导的过程可分为两个步骤：活化P₄以生成多磷配合物TM-Pₓ，以及随后对该配合物进行官能化以释放所需的含磷产物。到目前为止，前一步骤已经确立，能够分离出许多不同的TM-Pₓ产物。相比之下，这些配合物的有效官能化已被证明极具挑战性，仅在相对少数的情况下得以实现。在本综述中，我们全面总结了成功的TM-Pₓ官能化反应，其中TM-Pₓ必须通过TM前体与P₄反应获得。我们希望这将为致力于实现现代合成化学这一极具挑战性目标的持续努力提供有用的资源。
