Seiler Oliver, Burschka Christian, Fenske Tassilo, Troegel Dennis, Tacke Reinhold
Universität Würzburg, Institut für Anorganische Chemie, Am Hubland, D-97074 Würzburg, Germany.
Inorg Chem. 2007 Jun 25;46(13):5419-24. doi: 10.1021/ic700389r. Epub 2007 May 22.
The neutral heteroleptic hexacoordinate silicon(IV) complexes 4 and 5 (SiO(6) skeletons) and the neutral pentacoordinate silicon(IV) complexes 7-9 (SiO(4)N skeletons) were synthesized, starting from the hexacoordinate precursor 2 and the pentacoordinate precursor 6, respectively. In these reactions, two monoanionic cyanato-N ligands are replaced by one dianionic bidentate O,O-chelate ligand. Compounds 4, 5, and 7-9 were characterized by single-crystal X-ray diffraction and solid-state and solution NMR spectroscopy. The chiral silicon(IV) complexes 4, 5, 7, and 8 were obtained as racemic mixtures, whereas 9 was isolated as a cocrystallizate consisting of the two diastereomers, (C,S)-9 and (A,S)-9 (ratio 1:1). The stereodynamics of 5 and 8 were studied by variable-temperature (1)H NMR experiments.
中性异配位六配位硅（IV）配合物4和5（SiO(6)骨架）以及中性五配位硅（IV）配合物7 - 9（SiO(4)N骨架）分别从六配位前体2和五配位前体6开始合成。在这些反应中，两个单阴离子氰酸根 - N配体被一个双阴离子双齿O,O - 螯合配体取代。化合物4、5以及7 - 9通过单晶X射线衍射、固态和溶液核磁共振光谱进行了表征。手性硅（IV）配合物4、5、7和8以外消旋混合物形式获得，而9作为由两种非对映异构体（C,S）-9和（A,S）-9（比例1:1）组成的共结晶物被分离出来。通过变温（1）H NMR实验研究了5和8的立体动力学。
