Issue 47, 2019
From the journal:

Dalton Transactions

Solvent- and anion-dependent rearrangement of fluorinated carbene ligands provides access to fluorinated alkenes†

Lewis M. Hall,a   Lucy M. Milner,a   Sam J. Hart,a   Adrian C. Whitwood, ORCID logo a   Jason M. Lynam ORCID logo *a  and  John M. Slattery ORCID logo *a  

* Corresponding authors

a Department of Chemistry, University of York, Heslington, York, UK
E-mail: jason.lynam@york.ac.uk, john.slattery@york.ac.uk

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.

Graphical abstract: Solvent- and anion-dependent rearrangement of fluorinated carbene ligands provides access to fluorinated alkenes

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Article information

DOI
https://doi.org/10.1039/C9DT04307A
Article type
Paper
Submitted
11 Sep 2019
Accepted
07 Nov 2019
First published
08 Nov 2019

Dalton Trans., 2019,48, 17655-17659

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Solvent- and anion-dependent rearrangement of fluorinated carbene ligands provides access to fluorinated alkenes

L. M. Hall, L. M. Milner, S. J. Hart, A. C. Whitwood, J. M. Lynam and J. M. Slattery, Dalton Trans., 2019, 48, 17655 DOI: 10.1039/C9DT04307A

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