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Reversible Addition of Carbon Dioxide to Main Group Metal Complexes at Temperatures about 0 °C
Author(s) -
Koptseva Tatyana S.,
Sokolov Vladimir G.,
Ketkov Sergey Yu.,
Rychagova Elena A.,
Cherkasov Anton V.,
Skatova Alexandra A.,
Fedushkin Igor L.
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202004991
Subject(s) - chemistry , diethyl ether , cycloaddition , medicinal chemistry , toluene , ether , solvent , transition metal , acenaphthene , derivative (finance) , carbon dioxide , photochemistry , organic chemistry , catalysis , financial economics , economics , anthracene
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(CO 2 )Al‐Al(O 2 C)L] ( 2 ), whereas in diethyl ether, the reaction affords oxo‐bridged carbamato derivative [L(CO 2 )(Et 2 O)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 CO 2 . The optimized structures of key intermediates were obtained for the reactions in the presence of Et 2 O; calculated thermodynamic parameters unambiguously testify the irreversible formation of the product 3 .