The compounds Pn (pyS) 3 ( Pn = P, As, Sb, Bi) were synthesized from the respective chloride ( Pn = P, As, Sb) or nitrate (Bi), pyridine-2-thiol (pySH) and triethylamine (NEt 3 ) as a supporting base in THF (P, Sb), CHCl 3 (As) or methanol (Bi). Sb(pyS) 3 was also obtained from the reaction of SbCl 3 with LipyS (prepared in situ ) in methanol. The compounds Sb(pyS) 2 Ph and Sb(pyS)Ph 2 were prepared in a one-pot reaction starting from SbCl 3 and SbPh 3 (1:1 ratio). Upon Cl/pyS substitution, the resulting reaction mixture allows for a facile separation of the products in hot hexane. P(pyS) 3 and As(pyS) 3 crystallize isostructurally to the reported structure of Sb(pyS) 3 with κ -S-bound pyS ligands. These crystal structures feature close Pn ··· Pn contacts which are most pronounced for the arsenic derivative. Bi(pyS) 3 adopts a different molecular structure in the solid state, which features two chelating ( κ 2 -S,N-pyS) ligands and a κ -S-bound ligand. The presence of N→Bi interactions between the nitrogen atom of the κ -S-pyS ligand and the Bi atom of another molecule renders this structure a polymer chain along the crystallographic b axis with Bi⋅⋅⋅Bi van-der-Waals contacts. The structures of this set of Pn (pyS) 3 compounds were also studied in solution using 1 H NMR spectroscopy, revealing equivalent pyS ligands in discrete Pn (pyS) 3 molecules. The molecular structure of Sb(pyS)Ph 2 was optimized by quantum chemical methods, and a comparison with the structures reported for the other Sb/pyS/Ph combinations reveals Sb(pyS) 2 Ph to feature the strongest Sb···N interactions with the κ -S-pyS ligand. The results of 1 H NMR spectroscopic investigations of the compounds Sb(pyS) x Ph 3– x ( x = 3–0) suggest the Ph protons in ortho position to be incorporated into intramolecular C–H···S contacts for x = 2 and 1. Natural localized molecular orbital (NLMO) calculations were employed in order to gain insights into the electronic situations of the Pn atoms and Pn –R bonds (R = S, C), especially for the effects caused by formal substitution of Pn in the compounds Pn (pyS) 3 and the ligand patterns in the compounds Sb(pyS) x Ph 3– x ( x = 3–0). For the latter series of compounds, the electronic situation of the Sb atom was further studied by 121 Sb Mössbauer spectroscopy, providing a correlation between the calculated electron density at Sb [ ρ (0)] and the experimentally observed isomer shift δ . The missing link between group 15 and group 13 metal compounds of the type M (pyS) 3 , compound Al(pyS) 3 , was synthesized in this work. In the solid state (confirmed crystallographically), the mer isomer of this tris -chelate complex with distorted octahedral Al coordination sphere was found. This coordination mode was confirmed for the solution state (CDCl 3 ) by 1 H and 13 C NMR spectroscopy at T = −40 °C.

中文翻译：

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类型为Pn（pyS）3的化合物（Pn = P，As，Bi； pyS：吡啶-2-硫醇盐）和Sb（pyS）xPh3-x（x = 3-1）；Pn原子的分子结构和电子态

化合物Pn（pyS）3（Pn = P，As，Sb，Bi）由相应的氯化物（Pn = P，As，Sb）或硝酸盐（Bi），吡啶-2-硫醇（pySH）和三乙胺（ NEt 3）作为在THF（P，Sb），CHCl 3（As）或甲醇（Bi）中的支撑碱。还从SbCl 3与LipyS（原位制备）在甲醇中的反应获得Sb（pyS）3。以一锅法从SbCl 3和SbPh 3（1：1比例）开始制备化合物Sb（pyS）2 Ph和Sb（pyS）Ph 2。在Cl / pyS取代后，所得反应混合物允许在热己烷中容易地分离产物。P（pyS）3和As（pyS）3等价地结晶成具有κ-S结合pyS配体的Sb（pyS）3的结构。这些晶体结构具有紧密的Pn···Pn接触，这对于砷衍生物最为明显。Bi（pyS）3在固态时采用不同的分子结构，具有两个螯合的（κ2 -S，N-pyS）配体和一个与κ-S结合的配体。κ-S-pyS配体的氮原子与另一个分子的Bi原子之间存在N→Bi相互作用，使该结构沿着与Bi·⋅·Bi Van-der-Waals接触的晶体b轴成为聚合物链。还使用1 H NMR光谱在溶液中研究了这套Pn（pyS）3化合物的结构，揭示了离散Pn（pyS）3分子中的等价pyS配体。通过量子化学方法优化了Sb（pyS）Ph 2的分子结构，并与报道的其他Sb / pyS / Ph组合的结构进行了比较，发现Sb（pyS）2 Ph具有最强的Sb···N相互作用带有κ-S-pyS配体。化合物Sb（pyS）x Ph 3–x（x = 3-0）的1 H NMR光谱分析结果表明，邻位的Ph质子应结合到分子内C–H···S接触中，x = 2和1。使用自然局部分子轨道（NLMO）计算来深入了解Pn原子和Pn -R键（R = S，C）的电子状态，尤其是对于正式取代Pn所引起的影响化合物Pn（pyS）3中的配体和化合物Sb（pyS）x Ph 3–x（x = 3-0）中的配体模式。对于后面的一系列化合物，通过121 SbMössbauer光谱进一步研究了Sb原子的电子状态，从而提供了在Sb [ρ（0）]处计算出的电子密度与实验观察到的异构体位移δ之间的相关性。在这项工作中，合成了M（pyS）3类型的化合物Al（pyS）3的第15组和第13组金属化合物之间的缺失连接。在固态（通过晶体学确认）下，发现了具有扭曲的八面体Al配位球的三螯合物的三聚体异构体。在T = −40°C下，通过1 H和13 C NMR光谱法确认了溶液状态（CDCl 3）的这种配位模式。