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首页> 外文期刊>Chemistry: A European journal >Lower main-group element complexes with a soft scorpionate ligand: The structural influence of stereochemically active lone pairs
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Lower main-group element complexes with a soft scorpionate ligand: The structural influence of stereochemically active lone pairs

机译：具有软蝎子配体的下部主族元素配合物：立体化学活性孤对的结构影响

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摘要

The syntheses and structures of complexes of the fifth period elements indium and antimony, and the sixth period element bismuth with the soft scorpionate ligand, hydrotris(methimazolyl)borate (Tm-Me) are reported. A considerable variety of structural motifs were obtained by reaction of the main-group element halide and NaTmMe. The indium(III) complexes took the form [In(k(3)-Tm-Me)(2)](+). motif could not, however, be isolated for antimony(III), the dominant product being [Sb(k(3)-Tm-Me)(k(1)-Tm-Me)X] (X = Br, I). An iodo-bridged species [Sb(k(3)-Tm-Me)I(mu(2)-I)](2), analogous to a previously reported bismuth complex, was also isolated. Reaction of antimony(in) acetate with NaTmMe results in a remarkable species in which three different ligand binding modes are observed. In each antimony complex the influence of the nonbonded electron pair is observed in the structure. Bismuth halides form complexes analogous to those of antimony, with directional lone pairs, but in addition, reaction of Bi(NO3)(3) with NaTmMe results in a complex with a regular S-6 coordination sphere and a nonstereochemically active lone pair. Comparisons are drawn with known Tm-Me complexes of As, Sri, and Bi in which the stereochemical influence of the lone pairs is negligible and with Tm-Me complexes of Te and Bi in which the lone pairs are stereochemically active. This study highlights the ability of Tm-Me to coordinate in a variety of modes as dictated by the metal centre with no adverse effects on the stability of the complexes formed.
机译：报道了第五周期元素铟和锑，第六周期元素铋与软蝎子配体氢三（甲基咪唑基）硼酸酯（Tm-Me）的配合物的合成和结构。通过主族元素卤化物和NaTmMe的反应获得了相当多的结构基序。铟（III）配合物的形式为[In（k（3）-Tm-Me）（2）]（+）。但是，无法分离出锑（III）的基序，主要产物是[Sb（k（3）-Tm-Me）（k（1）-Tm-Me）X]（X = Br，I）。还分离了碘桥接的物质[Sb（k（3）-Tm-Me）I（mu（2）-I）]（2），类似于先前报道的铋配合物。乙酸锑（In）与NaTmMe的反应产生了一个非凡的物种，其中观察到了三种不同的配体结合模式。在每个锑配合物中，在结构中观察到非键合电子对的影响。卤化铋形成与锑类似的复合物，具有定向孤对，但此外，Bi（NO3）（3）与NaTmMe的反应产生具有规则S-6配位球和非立体化学活性孤对的复合物。与As，Sri和Bi的已知Tm-Me配合物（其中孤对的立体化学影响可以忽略）和Te和Bi的Tm-Me配合物（其中孤对具有立体化学活性）进行比较。这项研究强调了Tm-Me在金属中心规定的多种模式下进行配位的能力，而对形成的配合物的稳定性没有不利影响。

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