Mechanistic exploration of the copper(i) phosphide synthesis in phosphonium-based and phosphorus-free ionic liquids

Mai Lê Anh; Alexander Wolff; Martin Kaiser; Sivathmeehan Yogendra; Jan J Weigand; Julia Pallmann; Eike Brunner; Michael Ruck; Thomas Doert

doi:10.1039/c7dt03083e

Mechanistic exploration of the copper(i) phosphide synthesis in phosphonium-based and phosphorus-free ionic liquids

Dalton Trans. 2017 Nov 7;46(43):15004-15011. doi: 10.1039/c7dt03083e.

Authors

Mai Lê Anh¹, Alexander Wolff, Martin Kaiser, Sivathmeehan Yogendra, Jan J Weigand, Julia Pallmann, Eike Brunner, Michael Ruck, Thomas Doert

Affiliation

¹ Department of Chemistry and Food Chemistry, Technische Universität Dresden, 01062 Dresden, Germany. thomas.doert@tu-dresden.de.

PMID: 29051938
DOI: 10.1039/c7dt03083e

Abstract

The mechanism of the synthesis of copper(i) phosphide (Cu_3-xP) in the ionic liquid (IL) trihexyl(tetradecyl)phosphonium chloride ([P₆₆₆₁₄][Cl]) was investigated. The phosphide formation is promoted by a transformation of red phosphorus (P_red) into mobile P₄ molecules and a surface activation of copper caused by the IL including the Brønsted acidic impurity. The surface activation is important to obtain a quantitative product yield. Moreover, we demonstrate that single-phase Cu_3-xP can also be synthesized in the nitrogen-based IL tetrabutylammonium chloride ([N₄₄₄₄][Cl]). Further substitution of the anion of the IL using tetrabutylammonium bromide ([N₄₄₄₄][Br]) or the complete replacement of the IL by a deep eutectic solvent consisting of adipic acid and betaine do not lead to single-phase Cu_3-xP. Therefore, the nature of the anions present in the IL also seems to be relevant for the convenient phosphidization reaction.