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Highly Active Aluminium Catalysts for the Formation of Organic Carbonates from CO 2 and Oxiranes
Author(s) -
Whiteoak Christopher J.,
Kielland Nicola,
Laserna Victor,
CastroGómez Fernando,
Martin Eddy,
EscuderoAdán Eduardo C.,
Bo Carles,
Kleij Arjan W.
Publication year - 2014
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.201302536
Subject(s) - catalysis , chemistry , halide , ligand (biochemistry) , context (archaeology) , density functional theory , inorganic chemistry , lewis acids and bases , carbonate , ammonium , carbon dioxide , aluminium , organic chemistry , computational chemistry , paleontology , biochemistry , receptor , biology
Al III complexes of amino‐tris(phenolate) ligand scaffolds have been prepared to attain highly Lewis acidic catalysts. Combination of the aforementioned systems with ammonium halides provides highly active catalysts for the synthesis of organic carbonates through addition of carbon dioxide to oxiranes with initial turnover frequencies among the highest reported to date within the context of cyclic carbonate formation. Density functional theory (DFT) studies combined with kinetic data provides a rational for the relative high activity found for these Al III complexes, and the data are consistent with a monometallic mechanism. The activity and versatility of these Al III complexes has also been evaluated against some state‐of‐the‐art catalysts and the combined results compare favorably in terms of catalyst construction, stability, activity, and applicability.