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首页> 外文期刊>Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics >Synthesis of alkali metal indium thiophosphates containing the discrete anions [In(PS_4)(PS_5)_2]~(6-) and [In(PS_4)_2(PS_5)]~(6-)
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Synthesis of alkali metal indium thiophosphates containing the discrete anions [In(PS_4)(PS_5)_2]~(6-) and [In(PS_4)_2(PS_5)]~(6-)

机译：含有离散阴离子[In（PS_4）（PS_5）_2]〜（6-）和[In（PS_4）_2（PS_5）]〜（6-）的碱金属硫代磷酸铟的合成

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The first discrete anionic indium thiophosphate complexes are reported. The structures of K_6[In(PS_4)_(1.5)(PS _5)_(1.5)] (1), Rb_6[In(PS_4)(PS _5)_2] (2), and Cs_6[In(PS_4) _(1.5)(PS_5)_(1.5)] (3) all contain an anionic moiety consisting of octahedrally coordinated indium surrounded by the thiophosphate anions [PS_4]~(3-) and the new [PS_5]~(3-) ion. The conformation and bonding of the unsymmetric chelate ligand [PS _5]~(3-) to indium give rise to different anions of the general formula [In(PS_4)_(1+x)(PS_5) _(2-x)]~(6-) (x = 0, 0.5). The anionic moiety in K _6[In(PS_4)_(1.5)(PS_5)_(1.5)] (1) consists of cocrystallizing λ-[In(PS_4)_2(PS _5)]~(6-) and Λλδ-[In(PS _4)(PS_5)_2]~(6-) anions in a ratio of 1:1 (and their enantiomers). In Rb_6[In(PS_4)(PS _5)_2] (2), no cocrystallizatzion of anions was observed, and only the Λλλ-[In(PS_4)(PS_5) _2]~(6-) anion (and its enantiomer) is present. Cs _6[In(PS_4)_(1.5)(PS_5)_(1.5)] (3) shows the same disorder between [PS_4]~(3-) and [PS _5]~(3-) ions as in 1. In 3, however, the octahedrally coordinated indium atom and thiophosphate ligands form a Λδδ- [In(PS_4)(PS_5)_2]~(6-) anion cocrystallizing with δ-[In(PS_4)_2(PS _5)]~(6-). Additionally, ordered Rb_6[In(PS _4)(PS_5)_2] (2) was characterized by ~(31)P magic angle spinning NMR, Raman spectroscopy, UV-vis solid-state absorption spectroscopy, thermogravimetric analysis, differential thermal analysis, and energy dispersive X-ray analysis.
机译：报道了第一种离散的阴离子硫代磷酸铟络合物。 K_6 [In（PS_4）_（1.5）（PS _5）_（1.5）]（1），Rb_6 [In（PS_4）（PS _5）_2]（2）和Cs_6 [In（PS_4）_的结构（1.5）（PS_5）_（1.5）]（3）全部包含由被硫代磷酸根阴离子[PS_4]〜（3-）和新的[PS_5]〜（3-）离子包围的八面体配位的铟组成的阴离子部分。非对称螯合配体[PS _5]〜（3-）与铟的构象和键合产生不同通式的阴离子[In（PS_4）_（1 + x）（PS_5）_（2-x）] 〜（6-）（x = 0，0.5）。 K _6 [In（PS_4）_（1.5）（PS_5）_（1.5）]（1）中的阴离子部分由λ-[In（PS_4）_2（PS _5）]〜（6-）和Λλδ- [In（PS _4）（PS_5）_2]〜（6-）阴离子的比例为1：1（及其对映异构体）。在Rb_6 [In（PS_4）（PS _5）_2]（2）中，未观察到阴离子的共结晶，只有Λλλ-[In（PS_4）（PS_5）_2]〜（6-）阴离子（及其对映异构体）存在。 Cs _6 [In（PS_4）_（1.5）（PS_5）_（1.5）]（3）显示与[1]相同的[PS_4]〜（3-）和[PS _5]〜（3-）离子之间的无序。然而，在3中，八面体配位的铟原子和硫代磷酸盐配体形成Λδδ-[In（PS_4）（PS_5）_2]〜（6-）阴离子与δ-[In（PS_4）_2（PS _5）]共结晶。 6-）。此外，有序的Rb_6 [In（PS _4）（PS_5）_2]（2）的特征在于〜（31）P幻角旋转NMR，拉曼光谱，紫外可见固态吸收光谱，热重分析，差热分析，和能量色散X射线分析。

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