Details

Autor(en) / Beteiligte

• Schumann, Erik
• Brendler, Erica
• Böhme, Uwe
• Mertens, Florian

Titel

Synthesis of Aluminum N,N‐Dialkylcarbamates by Insertion of CO2 into Al−N Bonds

Ist Teil von

• European journal of inorganic chemistry, 2023-01, Vol.26 (2), p.n/a

Ort / Verlag

Weinheim: Wiley Subscription Services, Inc

Erscheinungsjahr

2023

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• Despite decades of research on various carbamates and their important applications, only one aluminum N,N‐dialkylcarbamate (ADC) with an aluminum:carbamate ratio of 1 : 3 has been structurally described and comprehensively studied so far, namely tris(diisopropyl)carbamate. The reasons for this situation include problems with the used synthetic routes. The process of CO2 insertion into Al−N bonds of tris(dialkylamido)alanes resolved these difficulties. Using this advantageous synthetic route, the dimethyl and diethyl, as well as the pyrrolidino, piperidino, and N‐methylpiperazino derivatives were now successfully prepared. These ADCs were investigated by solid‐state NMR spectroscopy, where line‐shape analyses of the 27Al NMR spectra allowed conclusions with respect to the determination of the quadrupole coupling parameters. Furthermore, data of an intermediate during the CO2 insertion into tris(diisopropylamido)alane were obtained by in‐situ IR spectroscopy, which were complemented by NMR measurements of samples periodically taken during the reaction. Partial hydrolysis of tris(pyrrolidino)carbamate revealed a complex Al3(μ3‐O) cluster structure, which was elucidated by single crystal X‐ray diffraction. A series of N,N‐dialkylcarbamates is synthesized by insertion of CO2 into Al−N bonds. Structural elucidation of these compounds was mainly performed by means of solid‐state NMR spectroscopy (27Al and 13C). Insights into the insertion mechanism were obtained by in‐situ IR and solution NMR spectroscopy conducted during the reaction. A partially hydrolyzed aluminum carbamate cluster was isolated and investigated by single crystal X‐ray diffraction.