Rhodehouse Melissa L, Smetana Volodymyr, Celania Chris, Mudring Anja-Verena, Meyer Gerd H
Department of Chemistry, Iowa State University, Ames, Iowa 50011, United States.
Ames Laboratory, USDOE, Iowa State University, Ames, Iowa 50011, United States.
Inorg Chem. 2020 May 18;59(10):7352-7359. doi: 10.1021/acs.inorgchem.0c00884. Epub 2020 May 7.
Starting generally with a 4:6:3 molar ratio of Pt, Sn, and (where = La-Sm), with or without the application of a NaCl flux, seven ternary compounds were obtained as single crystals. The platinides PtSnR ( = La-Nd) crystallize with the PtGePr type of structure (52, , = 27.6-27.8 Å, = 4.59-4.64 Å, = 9.33-9.40 Å). With = Pr, PtSnPr (52, , = 7.2863(3) Å, = 4.4909(2) Å, = 35.114(1) Å) is also obtained, which might be considered a high-temperature polymorph with disorder on the Sn- and Pr-sites. For = Nd and Sm, a structurally related isostructural series with a slightly different composition PtSn (52, 2, = 4.50-4.51 Å, = 26.14-26.30 Å, ≈ 7.29 Å) has been observed, together with PtSnSm (42, 2, = 4.3289(5) Å, = 28.798(4) Å, = 7.2534(9) Å) under the same conditions. The latter exhibits the rare ZrPdP-type structure, linking polar intermetallics to metal phosphides, in accord with PPdZr≡PtSnSm. All structures may be described in terms of either negative Pt/Sn networks encapsulating positive atoms, or {PtSn} clusters ( = 5, 6, or rarely 7) sharing vertices and edges with in the second coordination sphere and with considerable heterometallic Pt- bonding contributions.
通常从铂、锡和（其中 = 镧 - 钐）的4:6:3摩尔比开始，无论是否施加氯化钠助熔剂，都获得了七种三元化合物单晶。铂化物PtSnR（ = 镧 - 钕）以PtGePr型结构结晶（52， ， = 27.6 - 27.8 Å， = 4.59 - 4.64 Å， = 9.33 - 9.40 Å）。当 = 镨时，还获得了PtSnPr（52， ， = 7.2863(3) Å， = 4.4909(2) Å， = 35.114(1) Å），它可能被认为是一种在锡和镨位点上具有无序的高温多晶型物。对于 = 钕和钐，观察到了一个结构相关的同构系列，其组成略有不同，为PtSn（52，2， = 4.50 - 4.51 Å， = 26.14 - 26.30 Å， ≈ 7.29 Å），在相同条件下还有PtSnSm（42，2， = 4.3289(5) Å， = 28.798(4) Å， = 7.2534(9) Å）。后者呈现出罕见的ZrPdP型结构，将极性金属间化合物与金属磷化物联系起来，符合PPdZr≡PtSnSm。所有结构都可以用包裹正 原子的负Pt/Sn网络来描述，或者用在第二配位球中与 共享顶点和边且具有相当大的异金属Pt - 键贡献的{PtSn}簇（ = 5、6或很少为7）来描述。
