The azide ion can serve as a nitride source via N2 extrusion; analogous generation of P2 is explored both via niobium chemistry and photochemically starting from P4 (white phosphorus). Dibenzo-7-element norbornadiene molecules can serve as sources of reactive, unsaturated intermediates.  This is so within the protective coordination sphere of a transition metal, or without.  The synthesis and group transfer reactivity of a family of such molecules will be described.  In one case, a molecule viewed as a solid, crystalline adduct of nitrous oxide and anthracene serves as a thermally potent oxygen atom transfer (OAT) reagent.  Another example revolves around a method for terminal nitrido installation that is complementary to the use of azide, with anthracene instead of dinitrogen as the neutral leaving group.  Cyanonitrene [NCN] can also be delivered using such methodology.  Finally, the long-sought dibenzo-7-phosphanorbornadiene class of molecules has been obtained using a simple synthesis procedure, and they will be discussed in terms of structural considerations as well as for their potential to serve as sources of reactive phosphinidene intermediates.

Phosphorus intermediates inspired by organic azides

245th National Meeting (2013)

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