Reversible Addition of Carbon Dioxide to Main Group Metal Complexes at Temperatures about 0 °C.
Chemistry
; 27(18): 5745-5753, 2021 Mar 26.
Article
em En
| MEDLINE
| ID: mdl-33645870
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(O2 C)L] (2), whereas in diethyl ether, the reaction affords oxo-bridged carbamato derivative [L(CO2 )(Et2 O)Al(µ-O)AlL] (3). The DFT and QTAIM calculations provide reasonable explanations for the reversible formation of complexâ
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 Et2 O; calculated thermodynamic parameters unambiguously testify the irreversible formation of the productâ
3.
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Bases de dados:
MEDLINE
Idioma:
En
Revista:
Chemistry
Assunto da revista:
QUIMICA
Ano de publicação:
2021
Tipo de documento:
Article