CO(2) Capture with Silylated Ethanolamines and Piperazines

Amine treatment is commonly used to capture CO(2) from exhaust gases and from ambient air. The Si−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(2)‐insertion 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 −37 and −107 kJ mol(−1), while experimental values around −100 kJ mol(−1) were determined.