Neutral Hexacoordinate Silicon(IV) Complexes with a SiO4NC or SiO3N2C Skeleton and Neutral Pentacoordinate Silicon(IV) Complexes Containing a Trianionic Tetradentate O,N,O,O Ligand

Weiß, Jörg; Sinner, Katharina; Baus, Johannes A.; Burschka, Christian; Tacke, Reinhold

doi:10.1002/ejic.201301185

Cited by 16 publications

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References 42 publications

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“… 8 The increased stability of such derivatives based on tetradentate O 3 N-type ligands is a characteristic feature. Nevertheless, application of other ON-polydentate ligands for hypercoordinated Si compounds (like tridentate iminophenols, 9 tridentate alkanoloaminophenols, 10 tetradentate salens, 11 and others) is also known. Furthermore, there are several cases of application of other types of O 3 N ligands, like aminotrisphenols, 12 homotrialkanolamines, 13 and aminotris(alkylphenol)s 14 or alkanolaminobis(phenol)s 15 for Si derivatives.…”

Section: Introductionmentioning

confidence: 99%

Hypercoordinated Oligosilanes Based on Aminotrisphenols

et al. 2018

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The hypercoordinated silicon chlorides ClSi[(o-OC6H4)3N] (3) and ClSi[(OC6H2Me2CH2)3N] (5) were used for the synthesis of catenated derivatives (Me3Si)3SiSi[(o-OC6H4)3N] (9), (Me3Si)3SiSiMe2SiMe2Si(SiMe3)2Si[(o-OC6H4)3N] (11), and (Me3Si)3SiSi[(OC6H2Me2CH2)3N] (13) in reactions with (Me3Si)3SiK·THF (7) or (Me3Si)3SiK·[18-crown-6] (8). It was found that the nature of the (Me3Si)3SiK solvate determines the product of interaction, resulting in the formation of (Me3Si)3Si(CH2)4OSi[(OC6H2Me2CH2)3N] (12) or 13. Compounds obtained were characterized using multinuclear NMR and UV–vis spectroscopy and mass spectrometry. The molecular structures of 3, 9, and 11–13 were investigated by single-crystal X-ray analysis, featuring hypercoordinated Si atoms in a trigonal-bipyramidal coordination environment with O atoms in the equatorial plane. The structure of the side product [N(CH2C6H2Me2O)3Si]2O (6) was also studied, indicating highly tetrahedrally distorted trigonal-bipyramidal environment at the Si atoms, which was confirmed by crystal density functional theory calculations indicating the very weak Si ← N interaction. The Si···N interatomic distances span a broad range (2.23–2.78 Å). The dependence of structural and NMR parameters for hypercoordinated catenated compounds from the type of the ligand was established.

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Section: Introductionmentioning

confidence: 99%

Hypercoordinated Oligosilanes Based on Aminotrisphenols

et al. 2018

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2‐Acylpyrroles as Mono‐anionic O,N‐Chelating Ligands in Silicon Coordination Chemistry

Kämpfe

Brendler

Kroke

et al. 2014

Chemistry A European J

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Kryptopyrrole (2,4-dimethyl-3-ethylpyrrole) was acylated with, for example, benzoyl chloride to afford 2-benzoyl-3,5-dimethyl-4-ethylpyrrole (L(1)H). With SiCl4 this ligand reacts under liberation of HCl and formation of the complex L(1)2SiCl2. In related reactions with HSiCl3 or H2SiCl2, the same chlorosilicon complex is formed under liberation of HCl and H2 or liberation of H2, respectively. The chlorine atoms of L(1)2SiCl2 can be replaced by fluoride and triflate using ZnF2 and Me3Si-OTf, respectively. The use of a supporting base (triethylamine) is required for the complexation of phenyltrichlorosilane and diphenyldichlorosilane. The complexes L(1)2SiCl2, L(1)2SiF2, L(1)2Si(OTf)2, L(1)2SiPhCl, and L(1)2SiPh2 exhibit various configurations of the octahedral silicon coordination spheres (i.e. cis or trans configuration of the monodentate substituents, different orientations of the bidentate chelating ligands relative to each other). Furthermore, cationic silicon complexes L(1)3Si(+) and L(1) SiPh(+) were synthesized by chloride abstraction with GaCl3. In contrast, reaction of L(1)2SiCl2 with a third equivalent of L(1)H in the presence of excess triethylamine produced a charge-neutral hexacoordinate Si complex with a new tetradentate chelating ligand which formed by Si-templated C-C coupling of two ligands L(1).

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Novel Transition‐Metal (M=Cr, Mo, W, Fe) Carbonyl Complexes with Bis(guanidinato)silicon(II) Ligands

Mück

Kloß

Baus

et al. 2014

Chemistry A European J

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The donor-stabilized silylene 2 (the first bis(guanidinato)silicon(II) complex) reacts with the transition-metal carbonyl complexes [M(CO)6 ] (M=Cr, Mo, W) to form the respective silylene complexes 7-10. In the reactions with [M(CO)6 ] (M=Cr, Mo, W), the bis(guanidinato)silicon(II) complex 2 behaves totally different compared with the analogous bis(amidinato)silicon(II) complex 1, which reacts with [M(CO)6 ] as a nucleophile to replace only one of the six carbonyl groups. In contrast, the reaction of 2 leads to the novel spirocyclic compounds 7-9 that contain a four-membered SiN2 C ring and a five-membered MSiN2 C ring with a MSi and MN bond (nucleophilic substitution of two carbonyl groups). Compounds 7-10 were characterized by elemental analyses (C, H, N), crystal structure analyses, and NMR spectroscopic studies in the solid state and in solution.

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Neutral Hexacoordinate Silicon(IV) Complexes with a SiO₄NC or SiO₃N₂C Skeleton and Neutral Pentacoordinate Silicon(IV) Complexes Containing a Trianionic Tetradentate O,N,O,O Ligand

Cited by 16 publications

References 42 publications

Hypercoordinated Oligosilanes Based on Aminotrisphenols

Hypercoordinated Oligosilanes Based on Aminotrisphenols

2‐Acylpyrroles as Mono‐anionic O,N‐Chelating Ligands in Silicon Coordination Chemistry

Novel Transition‐Metal (M=Cr, Mo, W, Fe) Carbonyl Complexes with Bis(guanidinato)silicon(II) Ligands

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