Vibronic coupling

Cage-breaking cascade

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One-electron oxidation is generally expected to weaken a bond in a molecule or, on rare occasions, break it. Removing one electron from a small propellane cage has now been shown to break three lateral bonds, opening it up into an acyclic cation after a cascade of rearrangements, initiated by vibronic coupling.

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Figure 1: Oxidation of [1.1.1]propellane 1, leading to a primary radical cation 1+, which further rearranges to 3+ through a three-step process.

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Hiberty, P. Cage-breaking cascade. Nature Chem 3, 96–97 (2011) doi:10.1038/nchem.971

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