Mechanistic exploration of the copper(I) phosphide synthesis in phosphonium-based and phosphorus-free ionic liquids
The mechanism of the synthesis of copper(I) phosphide (Cu3−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 (Pred) 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 Cu3−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 Cu3−xP. Therefore, the nature of the anions present in the IL also seems to be relevant for the convenient phosphidization reaction.