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Mechanistic Exploration of the Copper(i) Phosphide Synthesis in Phosphonium-Based and Phosphorus-Free Ionic Liquids

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

Dalton Trans. 2017 Nov 7;46(43):15004-15011.

PMID: 29051938

Abstract:

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.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP654057973	Trihexyltetradecylphosphonium bromide		654057-97-3	Price

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