Zur Struktur der oktaedrischen Kationen cis‐[SiX2(bipy)2]2 +; die Kristallstruktur von [Si(OH)2(bipy)2]I2 · 2H2O

Sawitzki, Gisela; Kummer, D.; Seshadri, T.

doi:10.1002/cber.19781111114

Cited by 25 publications

(3 citation statements)

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“…To the best of our knowledge, only few molecular compounds exhibiting silanol water contacts by hydrogen bonding in the solid state were reported . In case of the [Si(OH) 2 (bipy) 2 ]I 2 ⋅2 H 2 O cation (bipy=bipyridyl), the SiOH absorption stretch appears at 3500‐3100 cm −1 …”

Section: Resultsmentioning

confidence: 99%

Reactivity of the Sterically Demanding Siloxanediol Mes₂Si(OH)(μ‐O)Si(OH)Mes₂ Towards Water and Ether Molecules

Roesch

Warzok

Enke

et al. 2017

Chemistry A European J

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A series of isotopologues of the siloxanediol Mes Si(OH)(μ-O)Si(OH)Mes (3 a) (Mes=2,4,6-trimethylphenyl) were synthesized by reactions of the corresponding disiloxane precursors Mes Si(μ-O) SiMes (2 a), Mes Si(μ- O) SiMes (2 b) or Mes Si(μ- O) SiMes (2 c) with an excess of H O, H O or H O. NMR and IR signal assignments for the siloxanediols in benzene are supported by quantum-chemical calculations, which indicate small energy differences between trans and cis conformers, the latter of which exhibits an intramolecular hydrogen bond. H NMR as well as IR data suggest the presence of a mixture of both conformers in C D . Hydrogen-bonded adducts of Mes Si(OH)(μ-O)Si(OH)Mes with ethers such as diethylether, dimethoxyethane or dioxane were observed in the solid state, where they form polymeric chain-like structures. The latter appear to be stable only in the crystal. O{ H} NMR and IR data in THF solution suggest an interaction of 3 a with at least one THF molecule, whereas diethylether appears not to interact. Water adducts form neither in solution nor in the solid state as indicated by NMR and ATR IR data. O{ H} NMR and ESI-MS experiments illustrate the remarkably high stability of the siloxanediols towards water and show no evidence for intra- or intermolecular oxygen-exchange reactions. In marked contrast, a stepwise exchange of all three oxygen atoms-including the one in the Si-O-Si bridge-occurred in the gas phase, when [Mes Si( OH)(μ- O)Si( O)Mes ] was treated with H O in the hexapole of an ESI FT-ICR mass spectrometer. The scrambling between the bridging and the other oxygen atoms likely proceeds through cyclic Si O intermediates.

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Section: Resultsmentioning

confidence: 99%

Reactivity of the Sterically Demanding Siloxanediol Mes₂Si(OH)(μ‐O)Si(OH)Mes₂ Towards Water and Ether Molecules

Roesch

Warzok

Enke

et al. 2017

Chemistry A European J

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“…The difficulty in oxidizing the catechol ligand in this silicon complex contrasts with the ruthenium analog, Ru(bpy) 2 (cat), which exhibits a reversible semiquinolate/catecholate wave at À0.73 V [13] (versus Fc + /Fc, converted from published SCE referenced data assuming Fc + /Fc is at +0.400 V versus SCE [14]). (2), Si-N2 1.953 (2), Si-N3 1.914 (2), Si-N4 1.955 (2), O1-Si-O2 100.67 (9). …”

Section: Resultsmentioning

confidence: 97%

“…Hexacoordinate bis(bipyridyl)silicon(IV) complexes have also been investigated recently, and it is likely that these complexes will demonstrate similar biological activity [7]. Currently, only five hexacoordinate bis(bipyridyl)silicon(IV) complexes appear in the Cambridge Structural Database: [Si(bpy) 2 (catecholato)] (PF 6 ) 2 [7], [Si(bpy) 2 (binolato)] (PF 6 ) 2 [7], [Si(bpy) 2 Cl 2 ]I 2 [8], [Si(bpy) 2 (OH) 2 ]I 2 [9], and Na[Si(bpy) 2 (dpcat-H)](ClO 4 ) 4 (dpcat-H = protonated dipyidocatecholate) [10]. In this paper we explore the electrochemical and structural properties of five bis(bipyridyl)silicon(IV) complexes: [Si(bpy) 2 (OMe) 2 ] 2+ (1), [Si(bpy) 2 (-OCH 2 CH 2 O-)] 2+ (2), [Si(bpy) 2 (OPh) 2 ] 2+ (3), [Si(bpy) 2 (bph)] 2+ (4), and [Si(bpy) 2 (cat)] 2+ (5), (bpy = 2,2 0 -bipyridine, cat = 1,2-benzenediolato, bph = 2,2 0 -biphenolato ligand).…”

Section: Introductionmentioning

confidence: 94%

Exploring the structure and redox activity of hexacoordinate bis(bipyridyl)silicon(IV) complexes

et al. 2015

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Silicon: Inorganic Chemistry

Lickiss

2005

Encyclopedia of Inorganic Chemistry

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Silicon is an element of vital importance in many areas of modern synthetic chemistry, the electronics industry and in materials science. This article attempts to summarize the many types of important inorganic derivatives of silicon but excludes the chemistry of silicates and zeolites, which are covered in separate articles. The isolation of elemental silicon from sand is described together with the various methods of purification of the element for use in the semiconductor industry. A brief description of the occurrence of silicon in biology is also given. The bulk of the article deals with compounds of silicon organized according to coordination number. One‐coordinate compounds are short‐lived intermediates and are described briefly. Two‐coordinate compounds, silylenes, have become increasingly important in recent years as are transition metal complexes in which they act as ligands. The use of bulky substituents has allowed stable silylenes to be isolated and their chemistry is described. Three‐coordinate compounds comprise radicals, cations, anions, and silanes (compounds containing a double bond to Si). These species are also generally short‐lived and reactive. The bulk of the article deals with four‐coordinate compounds and is organized according to the substituents at silicon. The industrially important hydrosilanes and halosilanes are described together with the mixed halohydrosilanes and the less common pseudohalosilanes. Alkoxysilanes are also industrially important and these are discussed with other oxygen derivatives such as esters and silanols. Compounds containing SiN bonds are also common and have interesting structural features. The preparation and structures of transition metal complexes containing silyl ligands is described. This is followed by a description of compounds containing silicon with coordination number five or six. The final section describes the analytical methods for the determination of the composition and structure of inorganic silicon compounds. Compounds containing SiC bonds are excluded throughout.

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Zur Struktur der oktaedrischen Kationen cis‐[SiX₂(bipy)₂]^{2 +}; die Kristallstruktur von [Si(OH)₂(bipy)₂]I₂ · 2H₂O

Cited by 25 publications

References 6 publications

Reactivity of the Sterically Demanding Siloxanediol Mes₂Si(OH)(μ‐O)Si(OH)Mes₂ Towards Water and Ether Molecules

Reactivity of the Sterically Demanding Siloxanediol Mes₂Si(OH)(μ‐O)Si(OH)Mes₂ Towards Water and Ether Molecules

Exploring the structure and redox activity of hexacoordinate bis(bipyridyl)silicon(IV) complexes

Silicon: Inorganic Chemistry

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Zur Struktur der oktaedrischen Kationen cis‐[SiX2(bipy)2]2 +; die Kristallstruktur von [Si(OH)2(bipy)2]I2 · 2H2O

Cited by 25 publications

References 6 publications

Reactivity of the Sterically Demanding Siloxanediol Mes2Si(OH)(μ‐O)Si(OH)Mes2 Towards Water and Ether Molecules

Reactivity of the Sterically Demanding Siloxanediol Mes2Si(OH)(μ‐O)Si(OH)Mes2 Towards Water and Ether Molecules

Exploring the structure and redox activity of hexacoordinate bis(bipyridyl)silicon(IV) complexes

Silicon: Inorganic Chemistry

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Product

Resources

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Zur Struktur der oktaedrischen Kationen cis‐[SiX₂(bipy)₂]^{2 +}; die Kristallstruktur von [Si(OH)₂(bipy)₂]I₂ · 2H₂O

Reactivity of the Sterically Demanding Siloxanediol Mes₂Si(OH)(μ‐O)Si(OH)Mes₂ Towards Water and Ether Molecules

Reactivity of the Sterically Demanding Siloxanediol Mes₂Si(OH)(μ‐O)Si(OH)Mes₂ Towards Water and Ether Molecules