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Selective CO 2 Splitting by Doubly Reduced Aryl Boranes to Give CO and [CO 3 ] 2−
Author(s) -
von Grotthuss Esther,
Prey Sven E.,
Bolte Michael,
Lerner HansWolfram,
Wagner Matthias
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201811135
Subject(s) - boranes , boron , aryl , medicinal chemistry , bond cleavage , chemistry , alkali metal , catalysis , metal , inorganic chemistry , stereochemistry , organic chemistry , alkyl
Alkali metal salts M 2 [ 1 ] (M=Li, Na) of doubly reduced 9,10‐dimethyl‐9,10‐dihydro‐9,10‐diboraanthracene ( 1 ) instantaneously add the C=O bond of CO 2 across their boron centers to furnish formal [4+2]‐cycloadducts M 2 [ 2 ]. If only 1 equiv of CO 2 is supplied, these products are stable. In the presence of excess CO 2 , however, C−O bond cleavage occurs and an O 2− equivalent is transferred to CO 2 to furnish CO and [CO 3 ] 2− . With M=Li, Li 2 CO 3 precipitates and the neutral 1 is liberated such that it can be reduced again to establish a catalytic cycle. With M=Na, [CO 3 ] 2− remains coordinated to both boron atoms in a bridging mode (Na 2 [ 4 ]). A mechanistic scenario is proposed, based on isolated intermediates and model reactions.