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Reversible structural rearrangement of π-expanded cyclooctatetraene upon two-fold reduction with alkali metals.

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The chemical reduction of a π-expanded COT derivative, octaphenyltetrabenzocyclooctatetraene (1), with lithium or sodium metals in the presence of secondary ligands affords a new doubly-reduced product (1TR2-). The X-ray diffraction… Click to show full abstract

The chemical reduction of a π-expanded COT derivative, octaphenyltetrabenzocyclooctatetraene (1), with lithium or sodium metals in the presence of secondary ligands affords a new doubly-reduced product (1TR2-). The X-ray diffraction study revealed a reductive core rearrangement accompanied by the formation of a single C-C bond and severe twist of the central tetraphenylene core. The reversibility of two-electron reduction and core transformation is further confirmed by NMR spectroscopy and DFT calculations.

Keywords: reversible structural; structural rearrangement; rearrangement expanded; expanded cyclooctatetraene; rearrangement; reduction

Journal Title: Chemical communications
Year Published: 2022

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