Facile storage and release of white phosphorus and yellow arsenic

Abstract

The storage of metastable compounds and modifications of elements are of great interest for synthesis and other, e.g., semiconductor, applications. Whereas white phosphorus is a metastable modification that can be stored under certain conditions, storage of the extremely (light- and air-)sensitive form of arsenic, yellow arsenic, is a challenge rarely tackled so far. Herein, we report on the facile storage and release of these tetrahedral E4 molecules (E = P, As) using activated carbon as a porous storage material. These loaded materials are air- and light-stable and have been comprehensively characterized by solid-state 31P{1H} MAS NMR spectroscopy, powder X-ray diffraction analysis, nitrogen adsorption measurements, and thermogravimetric analysis. Additionally, we show that these materials can be used as a suitable E4 source for releasing intact white phosphorus or yellow arsenic, enabling subsequent reactions in solution. Because the uptake and release of E4 are reversible, these materials are excellent carriers of these highly reactive modifications.

Regioselektive Insertion von Aluminium(I) in den cyclo‐P5‐Ring von Pentaphosphaferrocen

“…Luftstabile Polypnictogenkomplexe bieten sehr interessante Alternativen zu herkömmlich verwendetem, hochreaktivem P 4 als Ausgangsmaterialien für die Polypnictogenchemie . Kürzlich haben wir gezeigt, dass der cyclo ‐P 5 ‐Ring von [Cp*Fe(η 5 ‐P 5 )] als Polyphosphorquelle verwendet werden kann.…”

Regioselective Insertion of Aluminum(I) in the cyclo‐P5 Ring of Pentaphosphaferrocene

“…It is interesting to explore the scope of air‐stable starting materials as sources for poly‐pnictogen species as alternatives to the conventionally used and highly reactive P 4 . Recently, we have shown that the cyclo ‐P 5 ring of [Cp*Fe(η 5 ‐P 5 )] could be used as a polyphosphorous source.…”

Heavier pnictogens – treasures for optical electronic and reactivity tuning

“…These challenges have recently been addressed by the Scheer group, with a report detailing the preparation of activated carbon-supported As 4 and P 4 (As 4 @C and P 4 @C) which are air-and light-stable and which were employed as synthons in P 4 and As 4 activation chemistry. 18 While the synthesis of As 4 @C still requires the preparation of in situ As 4 solutions, the increased stability of As 4 @C is a marked improvement and has potential for the production of preparative-scale quantities.…”