Using the formation of strong oxo or imido bonds to niobium(V) as a driving force, unsaturated phosphorus-containing intermediates may be generated under mild conditions. Simple diatomic molecules including PP and AsP have been targeted for generation using such methodology, and information will be presented on their trapping reactions. Also targeted is an intermediate analogous to cyclobutadiene, with three of the ring carbons replaced by phosphorus. Finally, a Z-diphosphene as a cluster surface functional group is targeted and trapped in an overall synthesis of phosphorus-rich organic molecules stemming from white phosphorus, P4.