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Updated: Jan 31, 2026

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Structural and Electronic Effects of Stepwise Reduction of a Tetraaryl[3]Cumulene
Sarah N Spisak1, Martina U Bühringer2, Zheng Wei1
1Department of Chemistry, University at Albany, State University of New York, Albany, NY, 12222, USA.
Abstract:
The chemical reduction of a [3]cumulene ([3]TrTol) has been explored using alkali metals. Mono- and doubly reduced forms of [3]TrTol were isolated as solvent-separated ion pairs with {Na(18-crown-6)THF2 }+ and {K(18-crown-6)THF2 }+ counterions and crystallographically characterized. This allowed analysis of structural parameters of the "naked" anions of [3]TrTol without interference from metal binding. The dianion of [3]TrTol was also isolated as a contact-ion complex with {Cs(18-crown-6)}+ cations, thereby adding the effect of metal coordination to the core. Structural comparisons of anions to the neutral molecule, [3]TrTol, outline monotonic increases in bond-length alternation (BLA) upon stepwise reduction. The greatest BLA value is found for the contact-ion complex, which shows an alternating sequence of short and long carbon-carbon bonds, consistent with the structure of an alkyne. In contrast to studies on tetraphenyl[3]cumulene, the cumulenic framework of [3]TrTol remains planar in all the derivatives.
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