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Reduction vs. Addition: The Reaction of an Aluminyl Anion with 1,3,5,7‐Cyclooctatetraene
Author(s) -
Schwamm Ryan J.,
Anker Mathew D.,
Lein Matthias,
Coles Martyn P.
Publication year - 2019
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.201811675
Subject(s) - cyclooctatetraene , chemistry , stereochemistry , crystallography , molecule , ion , ligand (biochemistry) , aryl , potassium , medicinal chemistry , organic chemistry , alkyl , receptor , biochemistry
The potassium aluminyl complex K[Al(NON Ar )] (NON=NON Ar =[O(SiMe 2 NAr) 2 ] 2− , Ar=2,6‐ i Pr 2 C 6 H 3 ) reacts with 1,3,5,7‐cyclooctatetraene (COT) to give K[Al(NON Ar )(COT)]. The COT‐ligand is present in the asymmetric unit as a planar μ 2 ‐η 2 :η 8 ‐bridge between Al and K, with additional K⋅⋅⋅π‐aryl interactions to neighboring molecules that generate a helical chain. DFT calculations indicate significant aromatic character, consistent with reduction to [COT] 2− . Addition of 18‐crown‐6 causes a rearrangement of the C 8 ‐carbocycle to form the isomeric 9‐aluminabicyclo[4.2.1]nona‐2,4,7‐triene anion.