Unexpected Reactivity of Red Phosphorus in Ionic Liquids

Red phosphorus is far less reactive than the white allotrope. On the other hand, it is easier to handle and not as toxic as white phosphorus. In the Lewis‐acidic ionic liquid (IL) [BMIm]Cl·2AlCl3 ([BMIm] = 1‐butyl‐3‐methylimidazolium), red phosphorus and elemental iodine form several iodides at mode...

Full description

Saved in:
Bibliographic Details
Published in:European journal of inorganic chemistry 2015-08, Vol.2015 (24), p.3991-3994
Main Authors: Groh, Matthias F., Paasch, Silvia, Weiz, Alexander, Ruck, Michael, Brunner, Eike
Format: Article
Language:English
Subjects:
In situ spectroscopy
Iodides
Iodine
Ionic liquids
Monitoring
Nanoparticles
Nanostructure
NMR spectroscopy
Phosphorus
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:Red phosphorus is far less reactive than the white allotrope. On the other hand, it is easier to handle and not as toxic as white phosphorus. In the Lewis‐acidic ionic liquid (IL) [BMIm]Cl·2AlCl3 ([BMIm] = 1‐butyl‐3‐methylimidazolium), red phosphorus and elemental iodine form several iodides at moderate temperature. 31P liquid‐ and solid‐state NMR spectroscopy was used to rationalize the reaction at various temperatures and ratios of the starting materials. Monitoring of the reaction revealed nanoscale red‐phosphorus particles. In addition to this top‐down formation, phosphorus nanoparticles were also obtained in a bottom‐up synthesis by dissociation of P2I4 in the IL. Depending on the ratio of red phosphorus and iodine, as well as the reaction temperature, P2I4, PI3, or P2I5+ dominate. Red phosphorus readily reacts with iodine in a Lewis‐acidic ionic liquid at moderate temperature. Besides iodides, phosphorus nanoparticles are formed. The latter are also obtained in a bottom‐up process starting from P2I4. In situ liquid‐ and solid‐state NMR spectroscopy reveals details of the reactions.
ISSN:1434-1948
1099-0682
DOI:10.1002/ejic.201500502