A Mixed-Ring Sandwich Complex from Unexpected Ring
Contraction in [Re(η6‑C6H5Br)(η6‑C6R6)](PF6)

Alberto, Roger

A Mixed-Ring Sandwich Complex from Unexpected Ring Contraction in [Re(η⁶‑C₆H₅Br)(η⁶‑C₆R₆)](PF₆)

Version 2 2017-05-22, 19:33

Version 1 2017-05-11, 14:34

Posted on 2017-05-22 - 19:33

The contraction of coordinated aromatic hydrocarbons is a rare reactivity pattern in organometallic chemistry. We describe the conversion of a bromobenzene coordinated to a Re^I center into a cyclopentadienyl aldehyde. Under mildly alkaline conditions, the expected phenol complex is formed with Re and ⁹⁹Tc but under strong basic conditions; ring contraction occurs in close to quantitative yields for Re only. A mechanism for this unprecedented reaction is proposed based on ¹H and ²H NMR spectra and density functional theory calculations.

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Meola, Giuseppe; Braband, Henrik; Hernández-Valdés, Daniel; Gotzmann, Carla; Fox, Thomas; Spingler, Bernhard; et al. (2017). A Mixed-Ring Sandwich Complex from Unexpected Ring Contraction in [Re(η⁶‑C₆H₅Br)(η⁶‑C₆R₆)](PF₆). ACS Publications. Collection. https://doi.org/10.1021/acs.inorgchem.7b00394

https://doi.org/10.1021/acs.inorgchem.7b00394

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