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Thorium copper phosphides: more diverse metal–phosphorus and phosphorus–phosphorus interactions than U analogues

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Abstract

To explore the chemical analogy between thorium and heavier actinides in soft anionic environments, three new thorium phosphides (ThCuP2, β-ThCu2P2, and ThCu5P3) have been prepared through solid-state reactions using CuI as a reaction promoter. The structure of ThCuP2 can be described as a filled UTe2-type with both dimeric P24− and monomeric P3− anions, in which Th is coordinated by eight P atoms in a bicapped trigonal prismatic arrangement and Cu is tetrahedrally coordinated by four P atoms. β-ThCu2P2 contains only P3− anions and is isostructural with BaCu2S2. In this structure, Th is coordinated by seven P atoms in monocapped trigonal prismatic geometry and Cu is tetrahedrally coordinated by four P atoms. ThCu5P3 adopts the YCo5P3-type structure consisting of P3− anions. This structure contains Th atoms coordinated by six P atoms in a trigonal prismatic arrangement and Cu atoms that are either tetrahedrally coordinated by four P atoms or square pyramidally coordinated by five P atoms. Electric resistivity measurements and electronic structure calculations on β-ThCu2P2 indicate a metal. These new compounds may be charge-balanced and formulated as Th4+Cu+(P24−)1/2P3−, Th4+(Cu+)2(P3−)2, and Th4+(Cu+)5(P3−)3, respectively. The structural, bonding, and property relationships between these Th compounds and related actinide and rare-earth phases are discussed. Titled compounds display more diverse ion–ion interactions and different electronic structures from those in UCuP2 and UCu2P2 that were synthesized under similar experimental conditions, suggesting divergence of thorium-phosphide chemistry from uranium-phosphide chemistry.

Graphical abstract: Thorium copper phosphides: more diverse metal–phosphorus and phosphorus–phosphorus interactions than U analogues

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Publication details

The article was received on 12 Jun 2017, accepted on 26 Jul 2017 and first published on 26 Jul 2017


Article type: Paper
DOI: 10.1039/C7DT02145C
Citation: Dalton Trans., 2017, Advance Article
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    Thorium copper phosphides: more diverse metal–phosphorus and phosphorus–phosphorus interactions than U analogues

    G. B. Jin, C. D. Malliakas and J. Lin, Dalton Trans., 2017, Advance Article , DOI: 10.1039/C7DT02145C

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