Elemental Phosphorus and Electromagnetic Radiation

White phosphorus (P4) is a small molecule that is mainly used as a starting material for the large‐scale synthesis of most of the suitable phosphorus derivatives. The process starts with the direct reaction of P4 with Cl2, and the resulting phosphorus chloride is further treated with the adequate organic substrate. This industrial process is very primitive, and for economic and environmental reasons the first oxidation step should be avoided. The observation that the conversion of white P4 to the red allotrope is accelerated by ultraviolet light showed that the P4 molecule is able to be activated by electromagnetic radiation. Metal complexes can also mediate the functionalization of P4. The participation of electromagnetic radiation in the reactions that involve P4 and metal complexes has provided new procedures for obtaining new and interesting compounds that contain phosphorus atoms. Very significant and interesting reviews have summarized, classified and discussed the reactivity of P4 but until now none of them have distilled the relationship between white phosphorus and electromagnetic radiation. White phosphorus (P4) glows in the presence of air. It can also be activated by electromagnetic radiation, thereby providing a convenient way to obtain phosphorus‐containing compounds with and without metals. This microreview shows the most significant findings on the transformation of P4 under electromagnetic radiation.