Practical laboratory procedures now exist for the generation of organic derivatives of metaphosphoric acid (HO-PO 2 ), as well as for dioxophosphoranes (R-PO 2 ). These methods are evaluated in this review. Although these substances are highly reactive and have but a fleeting existence, they can nevertheless be employed as reactants in synthetic phosphorus chemistry. The various applications that have been demonstrated in the literature are also discussed in this review.