d6 metal systems for white phosphorus activation
Abstract This short review describes a breakthrough provided by the synthesis of d 6 metal complexes containing the intact molecules P 4 and P 4 S 3 . 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, PH 3 , such species as thiophosphinous acid, PH 2 SH, diphosphane, P 2 H 4 , 1-hydroxytriphosphane, PH(OH)PHPH 2 and 1,1,4-tris-hydroxytetraphosphane, P(OH) 2 PHPHPH(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 P 4 and P 4 S 3 cage molecules.