Reactions of CO2 and CO2 Analogs (CXY with X, Y=O, S, NR) with Reagents Containing Si–H and Si–N Units

Kraushaar, Konstantin; Schmidt, Dana; Schwarzer, Anke; Kroke, Edwin

doi:10.1016/b978-0-12-420221-4.00004-4

Cited by 32 publications

(24 citation statements)

References 161 publications

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“…The 29 Si NMR spectra of 1 with PhNCO show unreacted 3 and 1 and some minor signals. The insertion of PhNCO into 5 , 9 , and 13 leads to new signals in the 29 Si NMR spectra at δ = 13.8 ppm (insertion into 9 ) and 14.2 ppm (insertion into 5 ), next to the signals of 5 and 9 , respectively, which are in the typical range for insertion products of this type . The 13 C and 1 H NMR spectra show more new signals, which cannot be assigned.…”

Section: Resultsmentioning

confidence: 92%

“…The Si–N bond is prone towards hydrolysis and alkoholysis. Additionally, some substances containing Si–N bonds react with heteroallenes like CO 2 and isocyanates via insertion reactions yielding useful products such as ureas, carbamates, and polysiloxanes, among others . Therefore, in the presented study we have synthesized lactamomethylsilanes of the type Me x SiLac (4– x ) ( x = 0, 1, 2, and 3) [Lac = γ‐butyrolactam, δ‐valerolactam, ε‐caprolactam, and 1‐isoindolinone (phthalimidine)] in order to investigate their structures and reactivities.…”

Section: Introductionmentioning

confidence: 99%

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Lactamomethylsilanes – Synthesis, Structures, and Reactivity towards CO₂ and Phenylisocyanate

Herbig

Böhme

Kroke

2019

Zeitschrift anorg allge chemie

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Lactamomethylsilanes of γ-butyrolactam, δ-valerolactam, ε-caprolactam, and 1-isoindolinone (phthalimidine) with up to three methyl moieties were synthesized according to the chemical formula Me x SiLac (4-x) (x = 0, 1, 2, and 3). Using the lactams as starting materials four synthetic routes were tested: salt elimination, transsilylation, transamination, and metallation of the lactames followed by reaction 377 with methylchlorosilanes. All products were analyzed by NMR ( 1 H, 13 C and 29 Si) and RAMAN spectroscopy. Selected solid products were crystallized and the molecular structure was determined by single-crystal X-ray diffraction. The reactivity of the lactamomethylsilanes towards phenylisocyanate and CO 2 was studied.Si-O bond but less reactive than a Si-Cl bond. The Si-N bond is prone towards hydrolysis and alkoholysis. Additionally, some substances containing Si-N bonds react with heteroallenes like CO 2 and isocyanates via insertion reactions yielding useful products such as ureas, carbamates, and polysiloxanes, among others. [23][24][25][26] Therefore, in the presented study we have synthesized lactamomethylsilanes of the type Me x SiLac (4-x) (x = 0, 1, 2, and 3) [Lac = γ-butyrolactam, δ-valerolactam, εcaprolactam, and 1-isoindolinone (phthalimidine)] in order to investigate their structures and reactivities.

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Section: Resultsmentioning

confidence: 92%

Section: Introductionmentioning

confidence: 99%

Lactamomethylsilanes – Synthesis, Structures, and Reactivity towards CO₂ and Phenylisocyanate

Herbig

Böhme

Kroke

2019

Zeitschrift anorg allge chemie

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“…The first one consists in the insertion of a CO2 molecule into the Si-N bond of an in situ generated silylamine (Scheme 4, path a) [5,17,18,19]. This path requires a previous step consisting in a dehydrogenative silylation of the amine [20,21].…”

Section: Aminementioning

confidence: 99%

Rhodium-catalyzed formation of silylcarbamates from the reaction of secondary amines with CO2 and hydrosilanes

Guzmán

Torguet

Garcı́a-Orduña

et al. 2019

Journal of Organometallic Chemistry

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The reaction of (4-methyl-pyridine-2-iloxy)dimethylsilane (NSi Me-H, 1) with [RhCl(coe)2]2 gives the rhodium(III) complex [Rh(Cl)(κ 2-NSi Me)] (2), which reacts with a stoichiometric amount of AgCF3CO2 to afford [Rh(κ 2-CF3CO2)(κ 2-NSi Me)2] (3). Complexes 2 and 3 have been fully characterized by elemental analysis and NMR spectroscopy. The solid-state structure of 3 has been confirmed by X-ray diffraction analysis. Moreover, the activity of complex 3 as catalyst for the reaction of secondary amines with CO2 (3 bar) and hydrosilanes has been studied. The outcomes of these catalytic studies show that under these conditions complex 3 promotes the selective formation of silylcarbamates.

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“…In our previous investigations in the field of CO 2 absorption with aminosilanes, we have studied the silylation of various amines and other nitrogen containing organic compounds like lactams. Besides, we synthesised aminosilanes of the type R x Si (NHR') 4-x with up to four SiÀ N bonds per molecule. [2][3][4][5][6][7] Diaminosilanes R 2 Si(NHR') 2 allow quantitative twofold CO 2 insertion, successive thermolysis of the insertion products leads to ureas and oligosiloxanes.…”

Section: Introductionmentioning

confidence: 99%

“…Besides, we synthesised aminosilanes of the type R x Si (NHR') 4-x with up to four SiÀ N bonds per molecule. [2][3][4][5][6][7] Diaminosilanes R 2 Si(NHR') 2 allow quantitative twofold CO 2 insertion, successive thermolysis of the insertion products leads to ureas and oligosiloxanes. [4] Furthermore, we investigated the insertion reaction of other heteroallenes such as isocyanates and isothiocyanates into these aminosilanes.…”

Section: Introductionmentioning

confidence: 99%

CO₂ Capture with Silylated Ethanolamines and Piperazines

et al. 2019

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Amine treatment is commonly used to capture CO 2 from exhaust gases and from ambient air. The SiÀ N bond in aminosilanes is capable of reacting with CO 2 more readily than amines. In the current study we have synthesized trimethylsilylated ethanolamines, diethanolamines and piperazines and investigated their reaction toward CO 2. All products were characterized by 1 H, 13 C, and 29 Si NMR, RAMAN spectroscopy as well as mass spectrometry. The product of a twofold CO 2insertion into bis-trimethylsilylated piperazine was analysed by single-crystal X-ray diffraction. Furthermore, quantum chemical calculations (DFT) were used to supplement the experimental results. Geometry optimizations and NBO calculations for each starting material were carried out at the B3LYP level with different basis sets. DFT calculations at the B3LYP, WB97XD and M062x level were conducted for geometry optimization and frequency calculations to examine the thermochemical data. The calculations were carried out both for the gas phase and in solvent environment. The calculated reaction enthalpies varied between À 37 and À 107 kJ mol À 1 , while experimental values around À 100 kJ mol À 1 were determined.

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Reactions of CO2 and CO2 Analogs (CXY with X, Y=O, S, NR) with Reagents Containing Si–H and Si–N Units

Cited by 32 publications

References 161 publications

Lactamomethylsilanes – Synthesis, Structures, and Reactivity towards CO₂ and Phenylisocyanate

Lactamomethylsilanes – Synthesis, Structures, and Reactivity towards CO₂ and Phenylisocyanate

Rhodium-catalyzed formation of silylcarbamates from the reaction of secondary amines with CO2 and hydrosilanes

CO₂ Capture with Silylated Ethanolamines and Piperazines

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Reactions of CO2 and CO2 Analogs (CXY with X, Y=O, S, NR) with Reagents Containing Si–H and Si–N Units

Cited by 32 publications

References 161 publications

Lactamomethylsilanes – Synthesis, Structures, and Reactivity towards CO2 and Phenylisocyanate

Lactamomethylsilanes – Synthesis, Structures, and Reactivity towards CO2 and Phenylisocyanate

Rhodium-catalyzed formation of silylcarbamates from the reaction of secondary amines with CO2 and hydrosilanes

CO2 Capture with Silylated Ethanolamines and Piperazines

Contact Info

Product

Resources

About

Lactamomethylsilanes – Synthesis, Structures, and Reactivity towards CO₂ and Phenylisocyanate

Lactamomethylsilanes – Synthesis, Structures, and Reactivity towards CO₂ and Phenylisocyanate

CO₂ Capture with Silylated Ethanolamines and Piperazines