Hypervalent Silicon Compounds

Kost, Daniel; Kalikhman, I. D.

doi:10.1002/0470857250.ch23

Cited by 170 publications

(80 citation statements)

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“…Complex 2 exhibits a single signal by 31 . This shift to lower frequency parallels those typically observed for pentacoordinate neutral silicon adducts [11,20] and strongly suggests the presence of a gold!silane interaction in 2.…”

supporting

confidence: 82%

“…Heavier Group 14 elements such as silicon and tin are known to readily form hypervalent compounds through donor!acceptor interactions with organic Lewis bases. [11][12][13] A related situation is envisioned in complexes C, with a transition metal acting as a Lewis base. Such donor!…”

mentioning

confidence: 99%

“…Moreover, the Si À F bond is noticeably elongated upon coordination (from 1.600(2) in the free ligand 1 to 1.635(3) in complex 2), as observed in fluorosilane adducts with organic Lewis bases. [11,20] To confirm and further demonstrate the ability of saturated heavier Group 14 elements to behave as sacceptor ligands, the related tin complex 4 was then targeted. The Lewis acidity of Group 14 compounds towards organic Lewis bases increases on going from silicon to tin.…”

mentioning

confidence: 99%

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Gold–Silane and Gold–Stannane Complexes: Saturated Molecules as σ‐Acceptor Ligands

et al. 2009

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confidence: 82%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Gold–Silane and Gold–Stannane Complexes: Saturated Molecules as σ‐Acceptor Ligands

et al. 2009

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“…Compound 12 was isolated in 84% yield (1.62 g, 4.20 mmol) as a colorless crystalline product. M. p. 231°C, dec. [(Dimethylamino)methyl]trimethoxysilane (16). This compound was synthesized according to ref.…”

Section: Bis[benzohydroximato(2±)][3-(dimethylammonio)propyl]silicatementioning

confidence: 99%

Zwitterionic Spirocyclic λ5Si-Silicates with Two Bidentate Acetohydroximato(2-) or Benzohydroximato(2-) Ligands: Synthesis, Structure, and Dynamic Stereochemistry

Tacke

Bertermann

Biller

et al. 2000

Z. anorg. allg. Chem.

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The syntheses of the zwitterionic spirocyclic λ5Si‐silicates 7–14 are described. The chiral zwitterions contain a pentacoordinate (formally negatively charged) silicon atom and a tetracoordinate (formally positively charged) nitrogen atom, the ate and onium center being connected by an alkylene group. The zwitterions each contain two identical bidentate diolato(2–) ligands that formally derive from acetohydroximic acid or benzohydroximic acid. The stereochemistry and dynamic behavior of these compounds were investigated by experimental and theoretical methods. For this purpose, the zwitterionic λ5Si‐silicates 7–14 were studied by solution (1H, 13C, 29Si) and solid‐state (13C, 15N, and 29Si CP/MAS) NMR experiments. In addition, compounds 7, 8, 10, 11, and 13 were structurally characterized by single‐crystal X‐ray diffraction. The dynamic behavior (intramolecular enantiomerization) of 7 and 13 in solution was studied by VT 1H NMR experiments. These experimental studies were completed by ab initio investigations of the related anionic model species 15. The chiral compounds 7–14 exist as (λ)‐ and (δ)‐enantiomers in the solid state and in solution. The trigonal‐bipyramidal structure of the respective Si‐coordination polyhedra, with the two carbon‐linked oxygen atoms in the axial sites, is the energetically most favorable one. The (λ)‐ and (δ)‐enantiomers of 7–14 are configurationally stable in solution on the NMR time scale ([D6]DMSO, room temperature). They undergo an intramolecular (λ)/(δ)‐enantiomerization (twist‐type mechanism), with an activation free enthalpy of δG{ = 72–73 kJ mol–1 (experimentally established for 7 and 13; calculated energy barrier for the model species 15: 66.0 kJ mol–1).

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“…Oxalic Acid Bis(trimethylsilyl) Ester (16). Hexamethyldisilazane (14.1 g, 87.4 mmol) was added dropwise at room temperature within 10 min to a stirred suspension of oxalic acid (11.8 g, 131 mmol) in toluene (300 mL).…”

Section: Methodsmentioning

confidence: 99%

New Zwitterionic Spirocyclic λ5Si-Silicates with Two Ethane-1,2-diolato(2-), Oxalato(2-), or Benzene-1,2-diolato(2-) Ligands - Synthesis, Structure, and Dynamic Behavior

Tacke

Pülm

Richter

et al. 1999

Z. anorg. allg. Chem.

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Hypervalent Silicon Compounds

Cited by 170 publications

References 0 publications

Gold–Silane and Gold–Stannane Complexes: Saturated Molecules as σ‐Acceptor Ligands

Gold–Silane and Gold–Stannane Complexes: Saturated Molecules as σ‐Acceptor Ligands

Zwitterionic Spirocyclic λ5Si-Silicates with Two Bidentate Acetohydroximato(2-) or Benzohydroximato(2-) Ligands: Synthesis, Structure, and Dynamic Stereochemistry

New Zwitterionic Spirocyclic λ5Si-Silicates with Two Ethane-1,2-diolato(2-), Oxalato(2-), or Benzene-1,2-diolato(2-) Ligands - Synthesis, Structure, and Dynamic Behavior

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