Make it Double: [4]Cumulene Thermal Core Transformation and Chemical Reduction

Zheng Zhou; Zheng Wei; Matthew A. Johnson; Yikun Zhu; Yu Qiu; Rik R. Tykwinski; Marina A. Petrukhina

doi:10.1021/acs.orglett.5c03034

Make it Double: [4]Cumulene Thermal Core Transformation and Chemical Reduction

Zheng Zhou
, Zheng Wei
, Matthew A. Johnson
, Yikun Zhu
, Yu Qiu
, Rik R. Tykwinski
, Marina A. Petrukhina

Chemistry

University at Albany

SUNY Albany
Tongji University
University of Alberta

Research output: Contribution to journal › Article › peer-review

1 Scopus citations

Abstract

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 (2_TR^2–) crystallized as [Cs⁺(18-crown-6)₂][Cs⁺(2_TR^2–)]·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 2_TR^2–regenerated 1, demonstrating reversible cumulene–radialene interconversion.

Original language	English
Pages (from-to)	10993-10998
Number of pages	6
Journal	Organic Letters
Volume	27
Issue number	39
DOIs	https://doi.org/10.1021/acs.orglett.5c03034
State	Published - Oct 3 2025

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title = "Make it Double: [4]Cumulene Thermal Core Transformation and Chemical Reduction",

abstract = "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.",

author = "Zheng Zhou and Zheng Wei and Johnson, \{Matthew A.\} and Yikun Zhu and Yu Qiu and Tykwinski, \{Rik R.\} and Petrukhina, \{Marina A.\}",

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doi = "10.1021/acs.orglett.5c03034",

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TY - JOUR

T1 - Make it Double

T2 - [4]Cumulene Thermal Core Transformation and Chemical Reduction

AU - Zhou, Zheng

AU - Wei, Zheng

AU - Johnson, Matthew A.

AU - Zhu, Yikun

AU - Qiu, Yu

AU - Tykwinski, Rik R.

AU - Petrukhina, Marina A.

PY - 2025/10/3

Y1 - 2025/10/3

N2 - 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.

AB - 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.

UR - https://www.scopus.com/pages/publications/105017705808

U2 - 10.1021/acs.orglett.5c03034

DO - 10.1021/acs.orglett.5c03034

M3 - Article

C2 - 40985911

SN - 1523-7060

VL - 27

SP - 10993

EP - 10998

JO - Organic Letters

JF - Organic Letters

IS - 39

ER -

Make it Double: [4]Cumulene Thermal Core Transformation and Chemical Reduction

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