Beschreibung:
<jats:title>Abstract</jats:title><jats:p><jats:bold>Surrounded by six</jats:bold>: A series of novel neutral hexacoordinate silicon(<jats:sc>IV</jats:sc>) complexes with SiO<jats:sub>2</jats:sub>N<jats:sub>4</jats:sub> skeletons, containing two bidentate monoanionic O,N ligands and two monoanionic NCX (X = O, S) ligands, was synthesized. The formation of the title compounds involved some unexpected transformations of the bidentate O,N ligands.<jats:boxed-text content-type="graphic" position="anchor"><jats:graphic xmlns:xlink="http://www.w3.org/1999/xlink" mimetype="image/gif" position="anchor" specific-use="enlarged-web-image" xlink:href="graphic/mcontent.gif"><jats:alt-text>magnified image</jats:alt-text></jats:graphic></jats:boxed-text></jats:p><jats:p>A series of novel neutral hexacoordinate silicon(<jats:sc>IV</jats:sc>) complexes with SiO<jats:sub>2</jats:sub>N<jats:sub>4</jats:sub> skeletons (compounds <jats:bold>4</jats:bold>–<jats:bold>8</jats:bold>) was synthesized and structurally characterized by single‐crystal X‐ray diffraction and solid‐state NMR spectroscopy (<jats:sup>13</jats:sup>C, <jats:sup>15</jats:sup>N, <jats:sup>29</jats:sup>Si). The silicon(IV) complexes each contain two bidentate monoanionic O,N Schiff base ligands and two cyanato‐<jats:italic>N</jats:italic> or thiocyanato‐<jats:italic>N</jats:italic> ligands. Compounds <jats:bold>4</jats:bold>–<jats:bold>8</jats:bold> were prepared from Si(NCO)<jats:sub>4</jats:sub> or Si(NCS)<jats:sub>4</jats:sub>, whereby the complex formation involved some unexpected chemical transformations of the ligands.</jats:p>