Premium
Probing the Extremes of Covalency in M−Al bonds: Lithium and Zinc Aluminyl Compounds
Author(s) -
Roy Matthew M. D.,
Hicks Jamie,
Vasko Petra,
Heilmann Andreas,
Baston AnneMarie,
Goicoechea Jose M.,
Aldridge Simon
Publication year - 2021
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.202109416
Subject(s) - zinc , lithium (medication) , covalent bond , chemistry , magnesium , aluminium , nucleophile , crystallography , inorganic chemistry , computational chemistry , organic chemistry , catalysis , medicine , endocrinology
Synthetic routes to lithium, magnesium, and zinc aluminyl complexes are reported, allowing for the first structural characterization of an unsupported lithium–aluminium bond. Crystallographic and quantum‐chemical studies are consistent with the presence of a highly polar Li−Al interaction, characterized by a low bond order and relatively little charge transfer from Al to Li. Comparison with magnesium and zinc aluminyl systems reveals changes to both the M−Al bond and the (NON)Al fragment (where NON=4,5‐bis(2,6‐diisopropylanilido)‐2,7‐di‐tert‐butyl‐9,9‐dimethylxanthene), consistent with a more covalent character, with the latter complex being shown to react with CO 2 via a pathway that implies that the zinc centre acts as the nucleophilic partner.