Institut für Anorganische Chemie, Universität Würzburg , Am Hubland, 97074 Würzburg, Germany.
Inorg Chem. 2013 Sep 16;52(18):10664-76. doi: 10.1021/ic401698a. Epub 2013 Sep 6.
A series of neutral six-coordinate silicon(IV) complexes (4-11) with two bidentate monoanionic N,S-pyridine-2-thiolato ligands and two monodentate ligands R(1) and R(2) was synthesized (4, R(1) = R(2) = Cl; 5, R(1) = Ph, R(2) = Cl; 6, R(1) = Ph, R(2) = F; 7, R(1) = Ph, R(2) = Br; 8, R(1) = Ph, R(2) = N3; 9, R(1) = Ph, R(2) = NCO; 10, R(1) = Ph, R(2) = NCS; 11, R(1) = Me, R(2) = Cl). In addition, the related ionic compound 12 was synthesized, which contains a cationic five-coordinate silicon(IV) complex with two bidentate monoanionic N,S-pyridine-2-thiolato ligands and one phenyl group (counterion: I(-)). Compounds 4-12 were characterized by elemental analyses, NMR spectroscopic studies in the solid state and in solution, and crystal structure analyses (except 7). These structural investigations were performed with a special emphasis on the sophisticated stereochemistry of these compounds. These experimental investigations were complemented by computational studies, including bonding analyses based on relativistic density functional theory.
合成了一系列具有两个双齿单阴离子 N,S-吡啶-2-硫醇配体和两个单齿配体 R(1) 和 R(2) 的中性六配位硅(IV)配合物（4-11）（4，R(1) = R(2) = Cl；5，R(1) = Ph，R(2) = Cl；6，R(1) = Ph，R(2) = F；7，R(1) = Ph，R(2) = Br；8，R(1) = Ph，R(2) = N3；9，R(1) = Ph，R(2) = NCO；10，R(1) = Ph，R(2) = NCS；11，R(1) = Me，R(2) = Cl）。此外，还合成了相关的离子化合物 12，其包含阳离子五配位硅(IV)配合物，具有两个双齿单阴离子 N,S-吡啶-2-硫醇配体和一个苯基（抗衡离子：I(-)）。化合物 4-12 通过元素分析、固态和溶液中的 NMR 光谱研究以及晶体结构分析（除 7 外）进行了表征。这些结构研究特别强调了这些化合物复杂的立体化学。这些实验研究通过计算研究得到了补充，包括基于相对论密度泛函理论的键分析。
