Reproducibility of the cavity-modified silane deprotection rate
In plain words
The first widely cited claim of a dark cavity effect concerned a reaction that removes a silicon-containing group from a molecule. Independent groups have reported different results for the same reaction.
Precise statement
For the fluoride-induced desilylation of 1-phenyl-2-trimethylsilylacetylene in a Fabry-Perot cavity tuned to the Si-C stretch near $860\ \mathrm{cm}^{-1}$ or the Si-CH3 deformation near $1250\ \mathrm{cm}^{-1}$, determine whether the rate constant changes relative to detuned cavities by more than the combined experimental error, under controlled temperature and identical sample preparation. An answer is a yes or no from multi-laboratory measurements with shared protocols.
What would settle it
A round-robin measurement across several laboratories with identical cavities, reagents and temperature control.
Status in the literature
The original 2016 report (Thomas et al., Angew. Chem.) found a slowdown of several times; a 2021 replication attempt (Imperatore, Asbury, Giebink, J. Chem. Phys., https://doi.org/10.1063/5.0046307) found no cavity effect beyond error.
Related problems
- Special case of Reproducibility and artifacts in reported cavity rate changes · Silane deprotection is the flagship case of reproducibility of cavity rate claims
- Special case of Do cavity-coupled vibrations change thermal reaction rates