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Make it Double: [4]Cumulene Thermal Core Transformation and Chemical Reduction
Zheng Zhou1,2, Zheng Wei1, Matthew A Johnson3
1Department of Chemistry, University at Albany, State University of New York, Albany, New York 12222, United States.
None:
Heating of [4]cumulene 1 at 235 °C in vacuo affords the head-to-head [4]radialene dimer 2, which subsequently sublimes to produce single crystals. Reduction of 2 with Cs produced a ring-opened cumulene dimer dianion (2TR2-) crystallized as [Cs+(18-crown-6)2][Cs+(2TR2-)]·C6H14 (3). X-ray diffraction analysis revealed an unusual core transformation during the 2-fold reduction, with increased bond length alternation resembling an alkyne. Moreover, oxidation of 2TR2- regenerated 1, demonstrating reversible cumulene-radialene interconversion.
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