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Access to novel fluorovinylidene ligands via exploitation of outer-sphere electrophilic fluorination: New insights into C-F bond formation and activation

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JournalDalton Transactions
DateE-pub ahead of print - 24 Dec 2015
DatePublished (current) - 1 Jan 2016
Issue number4
Volume45
Number of pages10
Pages (from-to)1717-1726
Early online date24/12/15
Original languageEnglish

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(η5-C5H5)(PPh3)2(CC{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.

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© 2016, The Royal Society of Chemistry.

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