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.

中文翻译：

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磷化copper铜：比U类似物更多样化的金属磷和磷磷相互作用

探索钍和较重的锕系元素中软阴离子环境之间的化学类比，三个新的钍磷化物（ThCuP ₂，β-ThCu ₂ P ₂，和ThCu ₅ P ₃）已通过固态反应使用的CuI作为反应促进制备。ThCuP ₂的结构可以描述为具有二聚P ₂ ^4-和单体P ^3-阴离子的填充UTe ₂型，其中Th由两个P原子以二棱形三棱柱形排列，而Cu四面体由P组成。四个P原子。β-ThCu ₂ P ₂包含而仅为P ^3-阴离子，与BaCu ₂ S ₂同构。在这种结构中，Th由单封三角棱柱几何中的七个P原子配位，而Cu由四个P原子四面体配位。ThCu ₅ P ₃采用由P ³⁻阴离子组成的YCo ₅ P ₃型结构。该结构包含以三角形棱柱形排列由六个P原子配位的Th原子和由四个P原子四面体配位或由五个P原子四角锥配位的Cu原子。电阻率的测量和电子结构计算上β-ThCu ₂ P ₂表示金属。这些新化合物可以进行电荷平衡，并配制成Th ⁴⁺ Cu ⁺（P ₂ ⁴⁻）_1/2 P ³⁻，Th ⁴⁺（Cu ⁺）₂（P ³⁻）₂和Th ⁴⁺（Cu ⁺）₅（P ³⁻）₃。讨论了这些Th化合物与相关的act系元素和稀土相之间的结构，键和性质之间的关系。标题化合物与UCuP ₂和UCu相比，具有更多样化的离子-离子相互作用和不同的电子结构在相似的实验条件下合成的₂ P ₂，表明磷化th化学与铀化磷的化学反应有所不同。