Insertion of CO2 and related heteroallenes into the Si–N-bond of methyl(N-morpholino)silanes

Formation of Aromatic O‐Silylcarbamates from Aminosilanes and Their Subsequent Thermal Decomposition with Formation of Isocyanates

“…In the context of the more and more evolving topic of carbon dioxide utilization for the production of various crucial chemicals, we aim at employing CO 2 as an oxygen source as well as a carbon source in the synthesis of compounds such as (poly) siloxanes, urea derivatives and isocyanates. [1][2][3][4]5,6,7] One key step is the insertion reaction of CO 2 into SiÀ NR 1 R 2 bonds of aminosilanes with formation of the desired R 1 R 2 NC(O)OSi motif (cf. carbamoyloxysilane, carbamatosilane, O-silylcarbamate; Si = tetravalent silicon with three further substituents), as shown in Scheme 1.…”

“…Mechanistic considerations of the insertion of CO 2 into SiÀ N bonds have been published earlier. [1,6] In brief, at first a nucleophilic approach of the N atom toward the CO 2 carbon atom occurs. Two alternative proceeding routes arise depending on the nitrogen-bonded substituents.…”

CO2 Capture with Silylated Ethanolamines and Piperazines

“…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.…”

“…[4] Furthermore, we investigated the insertion reaction of other heteroallenes such as isocyanates and isothiocyanates into these aminosilanes. [4,5] The silylation of ethanolamines has been reported in older Russian literature, [8][9][10][11][12][13][14][15][16] which reports primarily on vibrational and NMR spectroscopic data of the silanes. Studies on carbon dioxide insertion reaction into the title compounds have not been published so far.…”

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

“…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.…”