A survey of the crystallographically determined structures of the Group 13 dithiophosphates and dithiophosphinates is presented with a focus upon both the molecular structures and supramolecular association involving the heavy element. Only small numbers of aluminium(III) (two) and gallium(III) (one) structures are known and these along with the 10 indium(III) examples have a preponderance towards homoleptic species with most coordination geometries based on an octahedron owing to the presence of symmetrically or almost symmetrically chelating phosphorodithiolato ligands; the notable exception is the gallium species which has an approximately tetrahedral geometry as two of the dithiophosphinate ligands coordinate in a monodentate mode. Diverse molecular structures are noted for the four heteroleptic examples of the lighter Group 13 elements which assemble in their crystals employing intermolecular interactions that do not involve the central element, as with the homoleptic structures. A completely different situation is evident for the thallium(I)/(III) structures which display a diverse array of coordination geometries and which usually assemble via Tl⋯S triel-bonding interactions; in the supramolecular assembly of thallium(I) crystals, Tl(lone-pair)⋯π(aryl) interactions are often observed.

中文翻译：

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第 13 族二硫代磷酸盐和二硫代次膦酸盐结构化学的文献调查


对 13 族二硫代磷酸盐和二硫代次膦酸盐的晶体学测定结构进行了调查，重点关注涉及重元素的分子结构和超分子缔合。仅已知少量铝 (III)（两个）和镓 (III)（一个）结构​​，这些结构与 10 个铟 (III) 示例一起，在大多数基于八面体的配位几何形状的均配物种中占优势，因为对称或几乎对称螯合二硫代磷酸配体的存在；值得注意的例外是镓物质，其具有近似四面体的几何形状，因为两个二硫代次膦酸盐配体以单齿模式配位。较轻的第 13 族元素的四个杂配例子具有不同的分子结构，它们利用不涉及中心元素的分子间相互作用在其晶体中组装，与同配结构一样。对于铊(I)/(III)结构来说，明显不同的情况是明显的，它们表现出多种配位几何形状，并且通常通过Tl⋯S triel键相互作用组装；在铊(I)晶体的超分子组装中，经常观察到Tl(孤对)⋯π(芳基)相互作用。