Equilibrium between neutral hexacoordinate silicon complexes and ionic pentacoordinate siliconium salts through fast dissociation–recombination of the Si–Cl bond

Kingston, Vijeyakumar; Gostevskii, B. A.; Kalikhman, I. D.; Kost, Daniel

doi:10.1039/b102427m

Cited by 36 publications

(13 citation statements)

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“…At higher temperatures the signal is shifted to higher field (e.g., δ =−111.2 ppm at 316 K). This counter‐intuitive temperature dependence (ionic dissociation upon cooling) has already been reported by Kost et al 3b. for complexes of the type ( O,N ) 2 SiPhCl (where ( O,N ) is a mono‐anionic hydrazide‐derived chelating ligand), and can be attributed to better anion solvation at lower temperatures.…”

Section: Resultssupporting

confidence: 63%

“…In the course of our investigations, we have studied silicon complexes with bi‐, tri‐, and tetradentate O , N ‐donor ligands,3b,c,f, 4a,b, 6 silicon complexes with five‐membered N ‐heterocyclic donor moieties,2g, h, 7 and other silicon compounds of pyrrole‐derived ligand systems 8. In the work reported herein, we now address silicon complexes with pyrrole‐functionalized bidentate O , N ‐chelating ligands.…”

Section: Introductionmentioning

confidence: 99%

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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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Section: Resultssupporting

confidence: 63%

Section: Introductionmentioning

confidence: 99%

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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“…To a solution of 0.8 g (2.2 mmol) of 7a in acetonitrile was added 0.85 g (4.3 mmol) of CF 3 SO 3 SiMe 3 . The reaction was boiled to reflux for 8 h and then cooled to room temperature.…”

Section: Methodsmentioning

confidence: 99%

Dinuclear Silicon Complexes of Uracil, Barbituric Acid, and 5,5-Dimethylbarbituric Acid: Hydrolytic Formation of Cyclic Oligomers

et al. 2010

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The synthesis and properties of dinuclear silicon complexes derived from uracil, barbituric acid, and 5,5-dimethylbarbituric acid, through the reaction with (chloromethyl)dimethylchlorosilane and (chloromethyl)dichloro(methyl)silane are described. The oxygen atoms are weakly coordinated to silicon in all three groups of compounds. Mild hydrolysis of the dinuclear compounds leads to formation of cyclic oligomers, with 2-9 monomer units in each, in which the individual units are connected through siloxane groups. Lithium chloride is shown to act as an effective template, restricting oligomerization to dimers and preventing higher-mass product formation.

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“…This occurs via an equilibrium for which there is a dramatic shift towards loss of Cl Ϫ as the temperature decreases. 174 It is suggested that the mechanism for the process might involve increasing solvent reorganisation around the ions or strengthening of the Si-N bond.…”

Section: -Co-ordinationmentioning

confidence: 99%

27 Mechanisms of reactions in solution

Davies¹

2002

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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Equilibrium between neutral hexacoordinate silicon complexes and ionic pentacoordinate siliconium salts through fast dissociation–recombination of the Si–Cl bond

Abstract: Equilibrium between neutral hexacoordinate silicon complexes and ionic siliconium chlorides, which is highly temperature, solvent, counterion, ligand and substituent dependent, was observed by low temperature 29 Si NMR and confirmed by crystal analysis.

Cited by 36 publications

References 9 publications

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

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

Dinuclear Silicon Complexes of Uracil, Barbituric Acid, and 5,5-Dimethylbarbituric Acid: Hydrolytic Formation of Cyclic Oligomers

27 Mechanisms of reactions in solution

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