Heteroallene Capture and Exchange at Functionalised Heptaphosphane Clusters

Area of Science:

• Inorganic chemistry
• Materials science
• Supramolecular chemistry

Background:

• Homoatomic seven-atom phosphorus clusters (P7) are known but their reactivity with small molecules is underexplored.
• Zintl-derived clusters offer unique structural and electronic properties for chemical applications.

Purpose of the Study:

• To investigate the reactivity of functionalized heptaphosphane cages with small molecules.
• To explore the potential of these clusters for small molecule capture and release.

Main Methods:

• Synthesis of neutral tris(silyl) functionalized heptaphosphane (P7(SiR3)3) cages.
• Reaction of the cages with various isocyanates and an isothiocyanate.
• Analysis of the regioselectivity of heteroallene capture at P-Si bonds.

Main Results:

• Heptaphosphane cages successfully capture heteroallenes (isocyanates, isothiocyanates) between P-Si bonds.
• Regioselective bonding of isocyanates is influenced by isocyanate functional groups and silyl substituents.
• Captured isothiocyanates can be exchanged for isocyanates, demonstrating a catch-and-release mechanism.

Conclusions:

• Functionalized phosphorus cages exhibit novel small molecule capture and release capabilities.
• These clusters show promise as chemical storage materials or reusable probes.