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Reversible Addition of Carbon Dioxide to Main Group Metal Complexes at Temperatures about 0 °C.
- Source :
- Chemistry - A European Journal; 3/26/2021, Vol. 27 Issue 18, p5745-5753, 9p
- Publication Year :
- 2021
-
Abstract
- The reaction of dialane [LAl‐AlL] (1; L=dianion of 1,2‐bis[(2,6‐diisopropylphenyl)imino]acenaphthene, dpp‐bian) with carbon dioxide results in two different products depending on solvent. In toluene at temperatures of about 0 °C, the reaction gives cycloadduct [L(CO2)Al‐Al(O2C)L] (2), whereas in diethyl ether, the reaction affords oxo‐bridged carbamato derivative [L(CO2)(Et2O)Al(μ‐O)AlL] (3). The DFT and QTAIM calculations provide reasonable explanations for the reversible formation of complex 2 in the course of two subsequent (2+4) cycloaddition reactions. Consecutive transition states with low activation barriers were revealed. Also, the DFT study demonstrated a crucial effect of diethyl ether coordination to aluminium on the reaction of dialane 1 with CO2. The optimized structures of key intermediates were obtained for the reactions in the presence of Et2O; calculated thermodynamic parameters unambiguously testify the irreversible formation of the product 3. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 09476539
- Volume :
- 27
- Issue :
- 18
- Database :
- Complementary Index
- Journal :
- Chemistry - A European Journal
- Publication Type :
- Academic Journal
- Accession number :
- 149695991
- Full Text :
- https://doi.org/10.1002/chem.202004991