title: Access to novel fluorovinylidene ligands via exploitation of outer-sphere electrophilic fluorination: new insights into C-F bond formation and activation.
abstract: Metal vinylidene complexes are widely encountered, or postulated, as intermediates in a range of important metal-mediated transformations of alkynes. However, fluorovinylidene complexes have rarely been described and their reactivity is largely unexplored. By making use of the novel outer-sphere electrophilic fluorination (OSEF) strategy we have developed a rapid, robust and convenient method for the preparation of fluorovinylidene and trifluoromethylvinylidene ruthenium complexes from non-fluorinated alkynes. Spectroscopic investigations (NMR and UV/Vis), coupled with TD-DFT studies, show that fluorine incorporation results in significant changes to the electronic structure of the vinylidene ligand. The reactivity of fluorovinylidene complexes shows many similarities to non-fluorinated analogues, but also some interesting differences, including a propensity to undergo unexpected C-F bond cleavage reactions. Heating fluorovinylidene complex [Ru(η(5)-C5H5)(PPh3)2(C[double bond, length as m-dash]C{F}R)][BF4] led to C-H activation of a PPh3 ligand to form an orthometallated fluorovinylphosphonium ligand. Reaction with pyridine led to nucleophilic attack at the metal-bound carbon atom of the vinylidene to form a vinyl pyridinium species, which undergoes both C-H and C-F activation to give a novel pyridylidene complex. Addition of water, in the presence of chloride, leads to anti-Markovnikov hydration of a fluorovinylidene complex to form an α-fluoroaldehyde, which slowly rearranges to its acyl fluoride isomer. Therefore, fluorovinylidenes ligands may be viewed as synthetic equivalents of 1-fluoroalkynes providing access to reactivity not possible by other routes.
authors.affiliation: Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK. jason.lynam@york.ac.uk john.slattery@york.ac.uk.
authors.forename: Lucy M
authors.initials: LM
authors.lastname: Milner
authors.affiliation: Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK. jason.lynam@york.ac.uk john.slattery@york.ac.uk.
authors.forename: Lewis M
authors.initials: LM
authors.lastname: Hall
authors.affiliation: Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK. jason.lynam@york.ac.uk john.slattery@york.ac.uk.
authors.forename: Natalie E
authors.initials: NE
authors.lastname: Pridmore
authors.affiliation: Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK. jason.lynam@york.ac.uk john.slattery@york.ac.uk.
authors.forename: Matthew K
authors.initials: MK
authors.lastname: Skeats
authors.affiliation: Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK. jason.lynam@york.ac.uk john.slattery@york.ac.uk.
authors.forename: Adrian C
authors.initials: AC
authors.lastname: Whitwood
authors.affiliation: Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK. jason.lynam@york.ac.uk john.slattery@york.ac.uk.
authors.forename: Jason M
authors.initials: JM
authors.lastname: Lynam
authors.affiliation: Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK. jason.lynam@york.ac.uk john.slattery@york.ac.uk.
authors.forename: John M
authors.initials: JM
authors.lastname: Slattery