Reduction of π-Expanded Cyclooctatetraene with Lithium: Stabilization of the Tetra-Anion through Internal Li+ Coordination

Zhou Z, Zhu Y, Wei Z, Bergner J, Neiß C, Doloczki S, Görling A, Kivala M, Petrukhina MA (2020)

Publication Type: Journal article

Publication year: 2020

Journal

Angewandte Chemie International Edition Wiley

Book Volume: 60

Pages Range: 3510-3514

Journal Issue: 7

DOI: 10.1002/anie.202013353

Abstract

The chemical reduction of a π-expanded polycyclic framework comprising a cyclooctatetraene moiety, octaphenyltetrabenzocyclooctatetraene, with lithium metal readily affords the corresponding tetra-anion instead of the expected aromatic dianion. As revealed by X-ray crystallography, the highly contorted tetra-anion is stabilized by coordination of two internally bound Li+, while two external cations remain solvent separated. The variable-temperature 7Li NMR spectra in THF confirm the presence of three types of Li+ ions and clearly differentiate internal binding, consistent with the crystal structure. Density-functional theory calculations suggest that the formation of the highly charged tetra-reduced carbanion is stabilized through Li+ coordination under the applied experimental conditions.

Authors with CRIS profile

Christian Neiß Lehrstuhl für Theoretische Chemie Susanne Doloczki Lehrstuhl für Organische Chemie I Andreas Görling Lehrstuhl für Theoretische Chemie

Involved external institutions

State University of New York at Albany (UNY Albany / UAlbany) US United States (USA) (US) Ruprecht-Karls-Universität Heidelberg DE Germany (DE)

How to cite

APA:

Zhou, Z., Zhu, Y., Wei, Z., Bergner, J., Neiß, C., Doloczki, S.,... Petrukhina, M.A. (2020). Reduction of π-Expanded Cyclooctatetraene with Lithium: Stabilization of the Tetra-Anion through Internal Li+ Coordination. Angewandte Chemie International Edition, 60(7), 3510-3514. https://dx.doi.org/10.1002/anie.202013353

MLA:

Zhou, Zheng, et al. "Reduction of π-Expanded Cyclooctatetraene with Lithium: Stabilization of the Tetra-Anion through Internal Li+ Coordination." Angewandte Chemie International Edition 60.7 (2020): 3510-3514.

BibTeX: Download