Recent developments in the solution-phase reactivity of trianionic heptaphosphide cages, P73-, have shown that such species can be used as sources of anionic polyphosphide moieties such as P3- and P5-. More recently, our research in this area has revealed that direct carbonylation of P73- affords the phosphaethynolate anion (PCO-; a phosphorous-containing analogue of cyanate). This species contains a highly reactive P-C multiple bond and can be employed as a ligand or as a precursor to novel phosphorus-containing compounds. For example, [2+2] cycloaddition reactions with heteroallenes (carbodiimides and isocyantes) give rise to four-membered rings containing a phosphide vertex.By analogy with W�hler's historic urea synthesis, direct reaction of PCO- with ammonium salts has been shown to yield phosphinecarboxamide (PH2C(O)NH2; Scheme 1), an air- and moisture-stable primary phosphine. This talk will focus on recent developments concerning the coordination chemistry and chemical reactivity of PCO- and PH2C(O)NH2.Scheme 1. Synthesis of phosphinecarboxamide by reaction of PCO- with NH4+ salts.

Novel organophosphorus species derived from anionic cage compounds

248th National Meeting (2014)

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