Synthesis and Structural Characterization of Neutral Hexacoordinate Silicon(<scp>IV</scp>) Complexes with SiO<sub>2</sub>N<sub>4</sub> Skeletons

Metz, Stefan; Burschka, Christian; Tacke, Reinhold

doi:10.1002/asia.200800405

Cited by 12 publications

References 35 publications

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Neutral Pentacoordinate Halogeno‐ and Pseudohalogenosilicon(IV) Complexes with an SiSONCX Skeleton (X=F, Cl, Br, I, N, C): Synthesis and Structural Characterization in the Solid State and in Solution

Metz

Theis

Burschka

et al. 2010

Chemistry A European J

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A series of neutral pentacoordinate silicon(IV) complexes with an SiSONCX skeleton (X=F, Cl, Br, I, N, or C) was synthesized and structurally characterized by multinuclear solution-state and solid-state NMR spectroscopy and single-crystal X-ray diffraction. These compounds contain an identical tridentate dianionic S,N,O ligand, a monodentate (pseudo)halogeno ligand (F, Cl, Br, I, NCS, N(3), or CN), and a monodentate organyl ligand (methyl, phenyl, 4-(trifluoromethyl)phenyl, or pentafluorophenyl). For most of these compounds, a dynamic equilibrium between the pentacoordinate silicon(IV) complex and two isomeric tetracoordinate silicon species in solution was observed. Most surprisingly, comparison of two series of analogous compounds containing fluoro, chloro, bromo, or iodo ligands demonstrated that pentacoordination in these series of silicon(IV) complexes is favored in the rank order I approximately Br>Cl>F; i.e., increasing the softness of the halogeno ligand favors pentacoordination.

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Neutral Pentacoordinate Halogeno‐ and Pseudohalogenosilicon(IV) Complexes with an SiSONCX Skeleton (X=F, Cl, Br, I, N, C): Synthesis and Structural Characterization in the Solid State and in Solution

Metz

Theis

Burschka

et al. 2010

Chemistry A European J

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Neutral Penta‐ and Hexacoordinate Silicon(IV) Complexes Containing Two Bidentate Ligands Derived from the α‐Amino Acids (S)‐Alanine, (S)‐Phenylalanine, and (S)‐tert‐Leucine

Cota

Beyer

Bertermann

et al. 2010

Chemistry A European J

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The neutral hexacoordinate silicon(IV) complex 6 (SiO(2)N(4) skeleton) and the neutral pentacoordinate silicon(IV) complexes 7-11 (SiO(2)N(2)C skeletons) were synthesized from Si(NCO)(4) and RSi(NCO)(3) (R = Me, Ph), respectively. The compounds were structurally characterized by solid-state NMR spectroscopy (6-11), solution NMR spectroscopy (6 and 10), and single-crystal X-ray diffraction (8 and 11 were studied as the solvates 8 x CH(3)CN and 11 x C(5)H(12) x 0.5 CH(3)CN, respectively). The silicon(IV) complexes 6 (octahedral Si-coordination polyhedron) and 7-11 (trigonal-bipyramidal Si-coordination polyhedra) each contain two bidentate ligands derived from an alpha-amino acid: (S)-alanine, (S)-phenylalanine, or (S)-tert-leucine. The deprotonated amino acids act as monoanionic (6) or as mono- and dianionic ligands (7-11). The experimental investigations were complemented by computational studies of the stereoisomers of 6 and 7.

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A Distorted Trigonal Antiprismatic Cationic Silicon Complex with Ureato Ligands: Syntheses, Crystal Structures and Solid State ²⁹Si NMR Properties

et al. 2010

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Keywords: Silicon / Chelates / Density-functional calculations / HypercoordinationInsertion of phenyl isocyanate into the Si-N bond of N-(trimethylsilyl)diethylamine yields the NЈ-silylated N,N-diethyl-NЈ-phenylurea 1, which undergoes transsilylation with SiCl 4 to yield the C 3 -symmetric cationic hexacoordinate silicon complex 3s + [tris-κ-O,NЈ-(N,N-diethyl-NЈ-phenylureato)siliconium] as chloride salt, which was characterized crystallographically. The cationic complex 3s + exhibits a distorted trigonal antiprismatic coordination sphere about the silicon atom with fac arrangement of the three N-atoms (and the three O-atoms) relative to one another. This C 3 -symmetric

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Synthesis and Structural Characterization of Neutral Hexacoordinate Silicon(IV) Complexes with SiO₂N₄ Skeletons

Cited by 12 publications

References 35 publications

Neutral Pentacoordinate Halogeno‐ and Pseudohalogenosilicon(IV) Complexes with an SiSONCX Skeleton (X=F, Cl, Br, I, N, C): Synthesis and Structural Characterization in the Solid State and in Solution

Neutral Pentacoordinate Halogeno‐ and Pseudohalogenosilicon(IV) Complexes with an SiSONCX Skeleton (X=F, Cl, Br, I, N, C): Synthesis and Structural Characterization in the Solid State and in Solution

Neutral Penta‐ and Hexacoordinate Silicon(IV) Complexes Containing Two Bidentate Ligands Derived from the α‐Amino Acids (S)‐Alanine, (S)‐Phenylalanine, and (S)‐tert‐Leucine

A Distorted Trigonal Antiprismatic Cationic Silicon Complex with Ureato Ligands: Syntheses, Crystal Structures and Solid State ²⁹Si NMR Properties

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Synthesis and Structural Characterization of Neutral Hexacoordinate Silicon(IV) Complexes with SiO2N4 Skeletons

Cited by 12 publications

References 35 publications

Neutral Pentacoordinate Halogeno‐ and Pseudohalogenosilicon(IV) Complexes with an SiSONCX Skeleton (X=F, Cl, Br, I, N, C): Synthesis and Structural Characterization in the Solid State and in Solution

Neutral Pentacoordinate Halogeno‐ and Pseudohalogenosilicon(IV) Complexes with an SiSONCX Skeleton (X=F, Cl, Br, I, N, C): Synthesis and Structural Characterization in the Solid State and in Solution

Neutral Penta‐ and Hexacoordinate Silicon(IV) Complexes Containing Two Bidentate Ligands Derived from the α‐Amino Acids (S)‐Alanine, (S)‐Phenylalanine, and (S)‐tert‐Leucine

A Distorted Trigonal Antiprismatic Cationic Silicon Complex with Ureato Ligands: Syntheses, Crystal Structures and Solid State 29Si NMR Properties

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Synthesis and Structural Characterization of Neutral Hexacoordinate Silicon(IV) Complexes with SiO₂N₄ Skeletons

A Distorted Trigonal Antiprismatic Cationic Silicon Complex with Ureato Ligands: Syntheses, Crystal Structures and Solid State ²⁹Si NMR Properties