d6 metal systems for white phosphorus activation

This short review describes a breakthrough provided by the synthesis of d6 metal complexes containing the intact molecules P4 and P4S3. The coordinated cage molecules acquire unexpected reactivity and undergo dismutation reactions in mild conditions in the presence of water. The outcomings are obtained either in form of free or coordinated molecules; the former are hypophosphorous and phosphorous acids, the latter comprise, besides phosphine, PH3, such species as thiophosphinous acid, PH2SH, diphosphane, P2H4, 1-hydroxytriphosphane, PH(OH)PHPH2 and 1,1,4-tris-hydroxytetraphosphane, P(OH)2PHPHPH(OH), which are either unknown or extremely reactive as free molecules. The formation of the above molecules provides a clue to the hydrolytic activation of the P4 and P4S3 cage molecules.