| Summary: | The controlled chemical activation of white phosphorus is a versatile, albeit often unpredictable, route to phosphorus containing species of varied nuclearities. The product distribution is particularly dependent on stoichiometry, temperature, and solvent. Low boiling point, highly polar solvents such as ammonia tend to favor formation of relatively small polyphosphides, whereas higher boiling or less polar solvents tend to favor formation of more highly aggregated anions. Binary solids and molecular anions are inextricably linked by both shared structural motifs and indeed the ability to extract solvated anions from the solid phases themselves. The chemistry of the polyarsenide, polystibide, and polybismuthide analogues is substantially less well developed, no doubt due to the lack of a suitable spectroscopic handle with which to monitor reactions.
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