Neutral
Six-Coordinate and Cationic Five-Coordinate
Silicon(IV) Complexes with Two Bidentate Monoanionic <i>N</i>,<i>S</i>‑Pyridine-2-thiolato(−) Ligands
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Abstract
A series
of neutral six-coordinate silicon(IV) complexes (<b>4</b>–<b>11</b>) with two bidentate monoanionic <i>N</i>,<i>S</i>-pyridine-2-thiolato ligands and two
monodentate ligands R<sup>1</sup> and R<sup>2</sup> was synthesized
(<b>4</b>, R<sup>1</sup> = R<sup>2</sup> = Cl; <b>5</b>, R<sup>1</sup> = Ph, R<sup>2</sup> = Cl; <b>6</b>, R<sup>1</sup> = Ph, R<sup>2</sup> = F; <b>7</b>, R<sup>1</sup> = Ph, R<sup>2</sup> = Br; <b>8</b>, R<sup>1</sup> = Ph, R<sup>2</sup> =
N<sub>3</sub>; <b>9</b>, R<sup>1</sup> = Ph, R<sup>2</sup> =
NCO; <b>10</b>, R<sup>1</sup> = Ph, R<sup>2</sup> = NCS; <b>11</b>, R<sup>1</sup> = Me, R<sup>2</sup> = Cl). In addition,
the related ionic compound <b>12</b> was synthesized, which
contains a cationic five-coordinate silicon(IV) complex with two bidentate
monoanionic <i>N</i>,<i>S</i>-pyridine-2-thiolato
ligands and one phenyl group (counterion: I<sup>–</sup>). Compounds <b>4</b>–<b>12</b> were characterized by elemental analyses,
NMR spectroscopic studies in the solid state and in solution, and
crystal structure analyses (except <b>7</b>). 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