The fluorine-NHC gauche effect: a structural and computational study

Paul, S., Schweizer, W.B., Rugg, G., Senn, H.M. and Gilmour, R. (2013) The fluorine-NHC gauche effect: a structural and computational study. Tetrahedron, 69(27-28), pp. 5647-5659. (doi: 10.1016/j.tet.2013.02.071)

75969.pdf - Accepted Version



Herein, we report the synthesis and X-ray structural analysis of a collection of fluorinated metal N-heterocyclic carbenes (Ag, Au, Pd, Rh, Ir) and their precursor salts. The common structural feature of these species is a flanking fluoroethyl group which is either freely rotating or embedded within a bicyclic framework. Solid state analysis confirmed a gauche conformational preference in all cases with the fluorine adopting a syn clinal arrangement (ϕ[NCCF] ~ 60°) with respect to the triazolium nitrogen at the vicinal position of the NHC. A density functional theory analysis was employed to quantify these effects and evaluate the influence of electronic modulation of the carbenic carbon [(C=N+); neutral carbene (C:); metal-bound carbene (C=M)], on the relative gauche / anti preference, thus highlighting the potential of this conformational phenomenon as a useful molecular design strategy for controlling the topology of organometallic complexes.

Item Type:Articles
Additional Information:NOTICE: this is the author’s version of a work that was accepted for publication in Tetrahedron. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Tetrahedron 69(27-28):5647-5659, 2013.
Glasgow Author(s) Enlighten ID:Senn, Dr Hans
Authors: Paul, S., Schweizer, W.B., Rugg, G., Senn, H.M., and Gilmour, R.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Tetrahedron
Published Online:01 March 2013
Copyright Holders:Copyright © 2013 Elsevier Ltd.
First Published:First published in Tetrahedron 69(27-28):5647-5659
Publisher Policy:Reproduced in accordance with the copyright policy of the publisher

University Staff: Request a correction | Enlighten Editors: Update this record

Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
518721Engineering and Physical Sciences Doctoral Training Grant 2009-13Mary GoodmanEngineering & Physical Sciences Research Council (EPSRC)EP/P504937/1VICE PRINCIPAL RESEARCH & ENTERPRISE
584861EPSRC Doctoral Training Grant 2011-2015Mary Beth KneafseyEngineering & Physical Sciences Research Council (EPSRC)EP/J500434/1VICE PRINCIPAL RESEARCH & ENTERPRISE