Transition‐Metal‐Mediated Functionalization of White Phosphorus

Recently there has been great interest in the reactivity of transition‐metal (TM) centers towards white phosphorus (P(4)). This has ultimately been motivated by a desire to find TM‐mediated alternatives to the current industrial routes used to transform P(4) 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(4) to generate a polyphosphorus complex TM‐P(n), 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(n) 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(n) functionalization reactions, where TM‐P(n) must be accessible by reaction of a TM precursor with P(4). We hope that this will provide a useful resource for continuing efforts that are working towards this highly challenging goal of modern synthetic chemistry.