Dimeric and trimeric diorganosilicon chalcogenides (PhRSiE)2,3 (E=S, Se, Te; R=Ph, Me)

Herzog, U.; Lange, Heike; Borrmann, Horst; Walfort, Bernhard; Lang, Heinrich

doi:10.1016/j.jorganchem.2004.06.068

Cited by 14 publications

(5 citation statements)

References 36 publications

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“…5,6 The THF solution of Li 2 S was prepared from sulfur and Li[B(Et) 3 H] according to the literature procedure and used in situ. 21 Preparation of (ArSbS) 2 (1). A solution of Li 2 S (4.38 mmol, prepared from 0.14 g of sulfur, and 8.8 mL of a 1 M THF solution of Li[B(Et) 3 H]) 21 in THF (20 mL) was added to a suspension of ArSbCl 2 22 (1.46 g, 3.81 mmol) in 3 mL of CH 2 Cl 2 .…”

Section: Methodsmentioning

confidence: 99%

“…21 Preparation of (ArSbS) 2 (1). A solution of Li 2 S (4.38 mmol, prepared from 0.14 g of sulfur, and 8.8 mL of a 1 M THF solution of Li[B(Et) 3 H]) 21 in THF (20 mL) was added to a suspension of ArSbCl 2 22 (1.46 g, 3.81 mmol) in 3 mL of CH 2 Cl 2 . Upon addition, the volume of the reaction mixture was reduced to ca.…”

Section: Methodsmentioning

confidence: 99%

“…Thermal analysis was performed with a Mettler DSC 12E Heat-Flux instrument. Starting compounds 1 and 2 were prepared by the reaction of the parent chlorides ArMCl 2 (M = Sb, Bi) with an in situ prepared THF solution of Li 2 S, which gives better yields in our hands than reactions using insoluble sodium sulfide (Scheme ). , The THF solution of Li 2 S was prepared from sulfur and Li[B(Et) 3 H] according to the literature procedure and used in situ …”

Section: Methodsmentioning

confidence: 99%

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[2 + 2] Cycloaddition of Carbon Disulfide to NCN-Chelated Organoantimony(III) and Organobismuth(III) Sulfides: Evidence for Terminal Sb−S and Bi−S Bonds in Solution

et al. 2010

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The organoantimony(III) and organobismuth(III) sulfides (LMS)2 (L = NCN chelating ligand, C6H3-2,6-(CH2NMe2)2; M = Sb (1), Bi (2)) are dimeric in the solid state. Nevertheless, their monomeric structures with terminal Sb−S and Bi−S bonds present in solution were trapped by [2 + 2] cycloaddition reactions with CS2, giving the molecular trithiocarbonates LMS2CS (M = Sb (3), Bi (4)). Both compounds were characterized in the solid state by X-ray diffraction techniques on both single crystals and powder material and by IR spectroscopy. Carbon disulfide can be easily eliminated from the trithiocarbonates 3 and 4 by heating to 120 °C (for 3) and 160 °C (for 4) to recover the starting sulfides 1 and 2. In solution, trithiocarbonates 3 and 4 exist in equilibrium with starting sulfides 1 and 2, but this equilibrium may be shifted to pure 3 and 4 by addition of an excess of CS2, as shown by 1H NMR spectroscopy.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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[2 + 2] Cycloaddition of Carbon Disulfide to NCN-Chelated Organoantimony(III) and Organobismuth(III) Sulfides: Evidence for Terminal Sb−S and Bi−S Bonds in Solution

et al. 2010

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“…Considering the toxicity of H 2 Se, we attempted to synthesize the selenium congener of 1 with dilithium selenide as a selenium source, which can be obtained from the reaction of elemental selenium with lithium triethylhydridoborate in THF. 8 Treatment of the in situ prepared dilithium selenide with one equivalent of 2 in THF at À78 1C, followed by protonation with two molar equivalents of trimethylammonium chloride, leads to a clear yellow solution, from which compound 3 could be isolated in the form of yellow crystals in 75% yield (Scheme 1).…”

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confidence: 99%

From elusive thio- and selenosilanoic acids to copper(i) complexes with intermolecular SiE → Cu–O–Si coordination modes (E = S, Se)

et al. 2013

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The facile synthesis of the first stable selenosilanoic acid-base adduct Using organic molecular defined species containing M-O-Si moieties as structural models for silica-supported metal/metal oxide catalysts has been proved to be a facile method to unravel the structure of a pre-catalyst as well as the mechanism of a catalytic reaction. 1 For example, the globular 56-membered copper(I) siloxane containing core made up of Cu-O-Si moieties (Chart 1), which is even soluble in organic solvents, could be prepared by the reaction of silanetriol with (MesCu) 4 (Mes = 2,4,6-Me 3 C 6 H 2 ). This copper siloxane cluster is active for the Ullmann-Goldberg-type C-N coupling reaction, 2 and can serve as a structural and functional model for silica-supported copper (pre)catalysts. In order to better understand the structurereactivity relationships of Cu-O-Si systems for various Cu-based chemical transformations, the synthesis of other types of Cu-O-Si containing compounds as structural and functional models for metallated terminal OH groups of silica surfaces is desired.Organic silanols have been reported to form well defined M-O-Si type compounds including silanediols, disiloxane-1,3-diols, silanetriols, trisiloxane-diol and silsesquioxane-triols (Chart 1). 1a,b,3,4 As possible intermediates involved in silica synthesis through hydrolysis of suitable silicon(IV) starting materials under acidic conditions, silicic acids, SiO x (OH) 4À2x , have not received much attention as precursors for the selective synthesis of M-O-Si compounds owing to their elusive nature. Likewise, organic silanoic acids RSi(QO)OH, the silicon analogues of carboxylic acids, represent elusive species which could only be studied at liquid nitrogen temperatures because of the presence of the highly polarized Si QO subunit which can undergo facile isomerisation or intermolecular head-to-tail polymerisation. 5 Recently, we reported the synthesis of the first isolable silanoic acid-base adducts, including the thiosilanoic system LSi(QS)OH(dmap) 1 (L = CH[C(Me)NAr] 2 , Ar = 2,6-iPr 2 C 6 H 3 , dmap = 4-dimethylaminopyridine) which is stabilised via hydrogen bonding to the pyridine N atom of dmap (Chart 1). 6 With these compounds in hand it became possible to employ 1 as a building block for Si(QS)-O-M formation. Accordingly, we reported the formation and reactivity of an isolable monomeric Si(QS)-O-Mn(II) complex. 7 Herein, we report the unexpectedly facile synthesis of the first isolable selenosilanoic acid-base adduct LSi( QSe)OH(dmap) 3 (Chart 1), and the Cu-metallation reactions of 1 and 3 with (MesCu) 4 to give the novel dimeric LSi(QE)OCu complexes 4 (E = S) and 5 (E = Se) with unprecedented intermolecular Si QE -Cu-O-Si coordination modes. In addition, their ability to serve as efficient pre-catalysts Chart 1

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“…87 Trimeric organosilicon chalcogenides are available from the reaction of Ph 2 SiCl 2 or PhMeSiCl 2 with lithium sulfide, selenide or telluride with twisted boat conformations typically observed. 88 From the same group, more than thirty new compounds are reported from the reaction of potassium hypersilylchalcogenates (K[ESi(SiMe 3 ) 3 ], E = S, Se, Te) with organochlorosilanes R 42x Si x (R = Me, Ph; x = 1-4) or Si 2 Me 5 Cl giving [(Me 3 Si) 3 SiE] x SiR 42x (x = 1-4) or [(Me 3 Si) 3 SiE] x Si 2 Me 62x (x = 1 or 2). 89 Two isomeric forms of (Me 5 Si 3 ) 2 S 3 are available from the reaction of 1,2,3trichloropentamethylsilane with H 2 S-Et 3 N, one a bicyclo[3.3.1]nonane type, the other with a bicyclo[3.3.2] skeleton, 29.…”

Section: Scheme 10mentioning

confidence: 99%

5 Carbon, silicon, germanium, tin and lead

Parr

2005

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

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Dimeric and trimeric diorganosilicon chalcogenides (PhRSiE)2,3 (E=S, Se, Te; R=Ph, Me)

Cited by 14 publications

References 36 publications

[2 + 2] Cycloaddition of Carbon Disulfide to NCN-Chelated Organoantimony(III) and Organobismuth(III) Sulfides: Evidence for Terminal Sb−S and Bi−S Bonds in Solution

[2 + 2] Cycloaddition of Carbon Disulfide to NCN-Chelated Organoantimony(III) and Organobismuth(III) Sulfides: Evidence for Terminal Sb−S and Bi−S Bonds in Solution

From elusive thio- and selenosilanoic acids to copper(i) complexes with intermolecular SiE → Cu–O–Si coordination modes (E = S, Se)

5 Carbon, silicon, germanium, tin and lead

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