title: Organometallic chemistry using partially fluorinated benzenes.
abstract: 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.
authors.affiliation: Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, UK. sp842@cam.ac.uk.
authors.forename: Sebastian D
authors.identifier: http://orcid.org/0000-0002-9791-5244
authors.initials: SD
authors.lastname: Pike
authors.affiliation: Department of Chemistry, Imperial College London, South Kensington, London SW7 2AZ, UK. m.crimmin@imperial.ac.uk.
authors.forename: Mark R
authors.identifier: http://orcid.org/0000-0002-9339-9182
authors.initials: MR
authors.lastname: Crimmin
authors.affiliation: Department of Chemistry, University of Warwick, Gibbet Hill Road, Coventry CV4 7AL, UK. a.b.chaplin@warwick.ac.uk.
authors.forename: Adrian B
authors.identifier: http://orcid.org/0000-0003-4286-8791
authors.initials: AB
authors.lastname: Chaplin