Make it Double: [4]Cumulene Thermal Core Transformation and Chemical Reduction
Heating of [4]cumulene <b>1</b> at 235 °C in vacuo affords the head-to-head [4]radialene dimer <b>2</b>, which subsequently sublimes to produce single crystals. Reduction of <b>2</b> with Cs produced a ring-opened cumulene dimer dianion (<b>2</b><sub><b>TR</b></sub><sup>2-</sup>) crystallized as [Cs<sup>+</sup>(18-crown-6)<sub>2</sub>][Cs<sup>+</sup>(<b>2</b><sub><b>TR</b></sub><sup>2-</sup>)]·C<sub>6</sub>H<sub>14</sub> (<b>3</b>). 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 <b>2</b><sub><b>TR</b></sub><sup>2-</sup> regenerated <b>1</b>, demonstrating reversible cumulene-radialene interconversion.
Authors
- Yikun Zhu (ORCID: https://orcid.org/0000-0003-0563-0127)
- Matthew A. Johnson (ORCID: https://orcid.org/0000-0001-5134-0986)
- Rik R. Tykwinski (ORCID: https://orcid.org/0000-0002-7645-4784)
- Zheng Yu Zhou (ORCID: https://orcid.org/0000-0001-8905-9663)
- Marina A. Petrukhina (ORCID: https://orcid.org/0000-0003-0221-7900)
- Zheng Wei (ORCID: https://orcid.org/0000-0003-4782-021X)
- Yu Qiu (ORCID: https://orcid.org/0009-0001-8168-9334)
Institutions
- Albany State University (US)
- Tongji University (CN)
- University of Alberta (CA)
- University at Albany, State University of New York (US)
Publication Details
- Journal
- Organic Letters
- Published
- 2025-09-23
- DOI
- https://doi.org/10.1021/acs.orglett.5c03034
- Citations
- 1
- Primary Topic
- Advanced Chemical Physics Studies
- Type
- article
- Field-Weighted Citation Impact
- 1.25