Transition Metal Functionalization of P₄ Using a Diarylgermylene Anchor

The manipulation of white phosphorus (P₄) has been a long-standing challenge for chemists. While the holy grail remains at finding a method to catalytically activate and functionalize P₄ to yield new organophosphorus compounds, fundamental research lies in developing procedures to control the reactivity of elemental phosphorus. In this work, Lewis acidic transition metal moieties M(CO)₅ (M = Cr, Mo, W) and AuCl react with P₄ derivatized with a low valent germanium compound. For both M(CO)₅ and AuCl, bis-functionalized products can be formed; however the monosubstituted derivatives are found to be more stable, and the decomposition can be monitored by ³¹P{¹H} NMR spectroscopy. The selective reactivity of white phosphorus, once a P-P bond has been activated, is a key step in yielding new organophosphorus compounds.