Phosphorus clusters are interesting because of their structural relationship to the heterogenous material red phosphorus. Red phosphorus is difficult to study and insoluble in common labratory solvents, while phosphorus clusters and in particular those that are functionalised are soluble. Hence, they can act as molecular models. Although known for decades, the chemical reactivity of homoatomic seven-atom phosphorus clusters ([P7]) towards small molecules remains largely unexplored. Reactivity uncovered with these cluster may reveal future applications for functionalised red phosphorus. We find that neutral tris(silyl) functionalised heptaphosphane (P7(SiR3)3) clusters are capable of heteroallene capture between the P−Si bonds of the cluster. A range of isocyanates and an isothiocyanate were investigated. In the case of isocyanates, silyl coordination at oxygen or nitrogen is regioselectively directed by the functional group on the isocyanate and substituents on the silyl moiety. Above all, we find that captured isothiocyanate molecules can be exchanged for isocyanate molecules, indicative of small molecule catch and release. Small molecule catch and release at these Zintl-derived clusters reveals their potential application as chemical storage materials or as reusable probes.

Heteroallene capture and exchange at functionalised heptaphosphane clusters

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