Polyphosphides are structurally-diverse clusters of phosphorus atoms that have attracted attention due to their fascinating chemistry, as well as their potential as materials for 2D semiconductors and lithium-ion battery anodes. Polyphosphides are typically produced in solid state from their elemental constituents or in complex solvent mixtures by the activation of hazardous, air-sensitive white phosphorus (P4). These methods hinder the access to large-scale synthesis of polyphosphides, which in turn deter both the exploratory chemistry and the potential uses of these fascinating structures. Herein, we report a convenient route to soluble polyphosphides through the unprecedented activation of shelf-stable red phosphorus with potassium ethoxide in a series of organic solvents. The synthesis of polyphosphides was scaled up to gram quantities by using a flow-chemistry process, and the resulting species were identified by 31P-NMR and X-ray structure determination. We have also prepared polyphosphides from an air-stable source of P4 that was obtained by loading this reactive form of phosphorus into a MOF through chemical vapor transport of red phosphorus. The loaded MOF can be successfully employed as a source of P4 in a series of reactions without the need to directly handle this air-sensitive material.

Versatile access to polyphosphides by solution- and flow-chemistry activation of red phosphorus

251st National Meeting (2016)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.