Hall, Lewis M., Milner, Lucy M., Hart, Sam J. et al. (3 more authors) (2019) Solvent- and anion-dependent rearrangement of fluorinated carbene ligands provides access to fluorinated alkenes. Dalton transactions (Cambridge, England : 2003). pp. 17655-17659. ISSN 1477-9234
Abstract
The construction of fluorocarbene ligands within the coordination sphere of transition metal complexes using sequential nucleophilic and electrophilic addition to a vinylidene complex is described. Reaction of [Ru(η5-C5H5)(dppe)([double bond, length as m-dash]C[double bond, length as m-dash]CPhF)][N(SO2Ph)2] with [NMe4]F results in nucleophilic attack of fluoride at the metal-bound carbon of the vinylidene ligand to give alkenyl complex [Ru(η5-C5H5)(dppe)(-CF[double bond, length as m-dash]CFPh)]. Subsequent eletrophilic fluorination with N-fluorobenzenesulfonimide (NFSI) results in the formation of the fluorinated carbene complex [Ru(η5-C5H5)(dppe)([double bond, length as m-dash]CF-CHFPh)][N(SO2Ph)2]. The fluorocarbene complexes undergo rearrangement to liberate free fluorinated alkenes, a process governed by the choice of solvent and anion, representing a new metal-mediated route to fluorinated alkenes from alkynes.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © The Royal Society of Chemistry 2019. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details. |
Dates: |
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Institution: | The University of York |
Academic Units: | The University of York > Faculty of Sciences (York) > Chemistry (York) |
Depositing User: | Pure (York) |
Date Deposited: | 16 Dec 2019 12:20 |
Last Modified: | 25 Jan 2025 00:09 |
Published Version: | https://doi.org/10.1039/c9dt04307a |
Status: | Published online |
Refereed: | Yes |
Identification Number: | 10.1039/c9dt04307a |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:154629 |