Reduction vs. Addition: The Reaction of an Aluminyl Anion with 1,3,5,7‐Cyclooctatetraene

Abstract

The potassium aluminyl complex K[Al(NONAr)] (NON=NONAr=[O(SiMe2NAr)2]2−, Ar=2,6‐iPr2C6H3) reacts with 1,3,5,7‐cyclooctatetraene (COT) to give K[Al(NONAr)(COT)]. The COT‐ligand is present in the asymmetric unit as a planar μ2‐η2:η8‐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 C8‐carbocycle to form the isomeric 9‐aluminabicyclo[4.2.1]nona‐2,4,7‐triene anion.

Reversible alkene binding and allylic C–H activation with an aluminium(i) complex

“…1). 31–33 For substrates with allylic C–H bonds, alkene binding is merely a precursor to non-reversible C–H activation. We show that, counter to the mechanism often proposed for transition metal systems, sequential binding and activation events do not involve bond breaking at the metal anchored substrate.…”

Substituent Effects on Aluminyl Anions and Derived Systems: A High-Level Theory

“…Catalyst IV was found to activate H 2 in benzene solution at ambient conditions or 2 atm of this gas in the solid state. Moreover, the activation of C–H bonds in benzene and formation of Al–Al and Al–Mg bonds were also observed. , Following this report, several stabilized aluminyl anions have been prepared to be subject to experimental and theoretical characterizations. − …”

Cubane Pyrolysis: Scaling Bond Polarity with Universal Polynomials

“…These three isomers have been extensively investigated by experimental and theoretical approaches due to their unique properties and potential applications. [18][19][20][21][22][23][24] https://doi.org/10.26434/chemrxiv-2023-kjrbc-v2 ORCID: https://orcid.org/0000-0001-5963-6028 Content not peer-reviewed by ChemRxiv. License: CC BY-NC-ND 4.0…”