Neutral Six-Coordinate and Cationic Five-Coordinate Silicon(IV) Complexes with Two Bidentate Monoanionic N,S-Pyridine-2-thiolato(鈭? Ligands

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• 作者：Johannes A. Baus ; Christian Burschka ; R眉diger Bertermann ; C茅lia Fonseca Guerra ; F. Matthias Bickelhaupt ; Reinhold Tacke
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：September 16, 2013
• 年：2013
• 卷：52
• 期：18
• 页码：10664-10676
• 全文大小：629K
• 年卷期：v.52,no.18(September 16, 2013)
• ISSN：1520-510X

文摘

A series of neutral six-coordinate silicon(IV) complexes (4鈥?b>11) with two bidentate monoanionic N,S-pyridine-2-thiolato ligands and two monodentate ligands R¹ and R² was synthesized (4, R¹ = R² = Cl; 5, R¹ = Ph, R² = Cl; 6, R¹ = Ph, R² = F; 7, R¹ = Ph, R² = Br; 8, R¹ = Ph, R² = N₃; 9, R¹ = Ph, R² = NCO; 10, R¹ = Ph, R² = NCS; 11, R¹ = Me, R² = 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^{鈥?/sup>). Compounds 4鈥?b>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.}