Organometallic chemistry using partially fluorinated benzenes
Royal Society of Chemistry
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Pike, S., Crimmin, M., & Chaplin, A. (2017). Organometallic chemistry using partially fluorinated benzenes. Chemical Communications, 53 (26), 3615-3633. https://doi.org/10.1039/c6cc09575e
Fluorobenzenes, in particular fluorobenzene (FB) and 1,2-difluorobenzene (1,2-DiFB), are increasingly becoming recognised as versatile solvents for conducting organometallic chemistry and transition-metal-based catalysis. The presence of fluorine substituents reduces the ability to donate π-electron density from the arene and consequently fluorobenzenes generally bind weakly to metal centres, allowing them to be used as essentially non-coordinating solvents or as readily displaced ligands. In this context, examples of well-defined complexes of fluorobenzenes are discussed, including trends in binding strength with increasing fluorination and different substitution patterns. Compared to more highly fluorinated benzenes, FB and 1,2-DiFB typically demonstrate greater chemical inertness, however, C–H and C–F bond activation reactions can be induced using appropriately reactive transition metal complexes. Such reactions are surveyed, including catalytic examples, not only to provide perspective for the use of FB and 1,2-DiFB as innocent solvent media, but also to highlight opportunities for their exploitation in contemporary organic synthesis.
We thank the Herchel Smith Fund (S. D. P.) and Royal Society (M. R. C., A. B. C.) for research fellowships. M. R. C. and A. B. C. also gratefully acknowledge the European Research Council for provision of Starting Grants (677367 and 637313) to support their current work on C–F and C–H bond activation, respectively.
External DOI: https://doi.org/10.1039/c6cc09575e
This record's URL: https://www.repository.cam.ac.uk/handle/1810/263498